Lecture-12
Characterization of Nanomaterials
(Structural Characterization, XRD)
(Ref: Guozhong Cao; Nanostructures & Nanomaterial: Synthesis, Properties & Applications)
Characterization and
Properties of Nanomaterials
• Nanomaterials & Nanostructures are characterized by:
- X-ray diffraction (XRD)
- Various Electron Microscopy (EM)
(i) Scanning Electron Microscopy (SEM)
(ii) Transmission Electron Microscopy (TEM)
(iii) Scanning Probe Microscopy (SPM)
• Chemical Characterization Techniques
- Optical Spectroscopy
- Electron Spectroscopy
- Ionic Spectrometry
• Relationships between physical properties and
Dimensions of nanomaterials are briefly discussed.
Structural Characterization
• Characterization of nanomaterials/nanostructures
- Surface Analysis Techniques, &
- Conventional Characterization Methods
• Similar to methods developed for bulk materials.
Example:
For nanoparticles, nanowires and thin films:
• XRD has been widely used for
- Determination of Crystallinity
- Crystal Structures, and
- Lattice Constants
• SEM & TEM together with Electron Diffraction
- Used in characterization of Nanoparticles.
• Optical spectroscopy is used to determine
- Size of Semiconductor Quantum Dots.
• SPM is relatively new characterization technique
- Found wide applications in Nanotechnology.
• Two major members of SPM family are
- Scanning Tunneling Microscopy (STM)
- Atomic Force Microscopy (AFM)
• STM & AFM are surface image techniques & can produce
- Topographic Images of surface
- Atomic resolution in all three dimensions
- Combining with appropriately designed attachments
• STM & AFM have broadened range of applications
- Nanoindentation
- Nanolithography
- Patterned Self-Assembly.
• Almost all solid surfaces, can be studied with STM & AFM
- Whether Hard or Soft
- Electrically Conductive or non-Conductive
• Surfaces can be studied in Air or Vacuum or Liquid.
X-ray diffraction (XRD)
• XRD is very important techniques to address issues
- Related to Crystal Structure of Solids
- Lattice Constants and Geometry
- Identification of Unknown Materials
- Orientation of Single Crystals
- Preferred Orientation of Polycrystals
- Defects, Stresses, etc.
Bragg’s Law
• X-rays (= 0.7-2 Å), incident on specimen, &
- Diffracted by crystalline phases of specimen
- In accordance to Bragg's law:
= 2d sin
‘d’ is spacing between atomic planes
‘’ is X-ray wavelength.
• Intensity of diffracted X-rays is measured as
- Function of the diffraction angle 2, &
- Specimen’s Orientation.
• Diffraction Pattern is used to identify
- Specimen’s Crystalline Phases, &
- To measure its structural properties.
• Diffraction peak positions are accurately measured with XRD
- Best method to characterize
(a) Homogeneous Strains
(b) Inhomogeneous Strains.
• Homogeneous or Uniform Elastic Strain
- Shifts the diffraction peak positions.
• From shift in peak positions, one can calculate
- Change in d-spacing (Occurs due to change of lattice constants under strain)
• Inhomogeneous strains vary from
- Crystallite to Crystallite
or
- Within a single crystallite
• This causes broadening of diffraction peaks &
- Increases with sin .
• Peak broadening is also caused by
- Finite size of crystallites
• Here the broadening is independent of sin
• When both crystallite size & inhomogeneous strain
- Contribute to the peak width
• It can be separately determined by
- Careful analysis of peak shapes
• If there is no In-Homogeneous strain,
- Crystallite size, ‘D’, can be estimated from peak width
- Using Scherrer's formula:
Kλ
D=
B cos θB
Where; ‘’ is the X-ray wavelength
‘B’ is full width half maximum (FWHM) (Diffraction Peak)
‘B’ is the diffraction angle, and
‘K’ is the Scherrer’s constant (Order of unity for usual crystal)
• Nanoparticles often form twinned structures
• Therefore, Scherrer’s formula may produce results
- Different from the true particle sizes.
• In addition, X-ray diffraction only provides
- Collective information of the particle sizes, &
- Usually requires a sizable amount of powder.
• It should be noted that estimation would work
- Only for very small particles
• Technique is very useful in
- Characterizing nanoparticles
• Similarly, film thickness can also be estimated for
- Epitaxial & highly textured thin films with XRD
Powder X-ray diffraction of a series of InP nanocrystal sizes.
The stick spectrum gives the bulk reflections with relative intensities.
[A.A. Guzelian et.al., J. Phys. Chem., 100(1996)7212]
• Disadvantages of XRD, (Compared to Electron Diffraction)
- Low intensity of diffracted X-rays
- Particularly for low-Z materials
• XRD is more sensitive to high-Z materials
• For low-Z materials
- Neutron or Electron diffraction is more suitable
• Typical intensities for Electron Diffraction are
- 108 times larger than XRD
- Because of small diffraction intensities
• XRD generally requires large specimens
• Information acquired is an average over a large
amount of material
Prof. S. K. Tripathi
Department of Physics
School of Physical Sciences
Mahatma Gandhi Central University
Course Name: Nano Materials and Applications
Course Code: PHYS3024
