Methods for Crystallographic Characterization

Yi Ding

1 February 2005

Outline
Introduction to x-ray diffraction Bragg's law Powder diffraction Thin film diffraction
Rocking curve measurements Grazing incidence x-ray diffraction measurements Texture measurements

Small angle x-ray scattering (SAXS) Other techniques (electron diffraction, neutron scattering) Summary
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Introduction to XRD
X-ray generation: x-ray tubes or synchrotron radiation Wavelength: a few angstroms to 0.1 angstrom, comparable to lattice constants X-rays can penetrate deep: bulk structure X-ray diffraction comes from the interference of the scattered x-ray due to the periodicity of the lattice

Braggs Law

2dsin=n,
where d is the inter-plane distance, is the scattering angle, n is the order of the diffraction and is the wavelength of the x-ray.

d

Powder Diffraction
The sample is in a powdery form, consisting of about 106 to 1012 crystallites Crystallites are still big enough to diffract x-ray All crystallites are randomly oriented Scan the detector to record all diffraction peaks, both transmission and reflection geometry are possible Use the positions and the intensities of the peaks to identify the structure of the material PDF data and computer software are available

Thin Film Diffraction

XRD can be used to investigate both thin film and the substrate Normally reflection geometry is used High angular resolution is needed
Monochromators are used Accurate angular controls are needed

Several techniques are widely used for thin film

Rocking curve measurements Grazing incidence x-ray diffraction measurements Texture measurements

Rocking Curve
The detector is fixed at 2 position The sample is scanned around The defects in the sample will cause the width of the peak broaden Rocking curve is usually used to indicate the quality of the thin film tor tec De

Grazing Incidence X-ray Diffraction

The incident x-ray is fixed at a very small angle with respect to the sample surface The detector does 2 scan Parallel x-ray beam is used Grazing incidence x-ray diffraction is usually used to study the surface of the sample
ete D
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tor c

Texture Measurement
A texture measurement is also called a pole figure It is plotted in polar coordinates around a given crystallographic orientation The detector is fixed at 2 position The sample is scanned by in-plane rotation around the plane normal at different azimuthal angles Texture measurement is used to determine the orientation distribution in a polycrystalline sample

Small Angle X-ray Scattering

SAXS technique is commonly used for large length scale structures such as self-assembled superlattices From Braggs law, 2dsin=n, the scattering angle will be small for the same x-ray wavelength if the periodicity is large SAXS typically has scattering angle 2<1 Due to the small angular separation of the direct beam and the scattered beam, to achieve good signal-to noise ratio:
Large sample-to-detector distances High quality collimating optics

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Other Techniques
Electron diffraction has shorter wavelength, thus smaller diffraction angle Electrons interact stronger than x-ray, can be used to study small areas Low energy electron diffraction (LEED) can be used to study the surface and has a long wavelength Neutron scattering is weak, and less accessible, but can detect the magnetic structure of the sample

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Summary
X-ray diffraction is the main method for crystallographic characterization for both bulk and thin film materials Electron diffraction and neutron diffraction have unique advantages and are very important supplements to XRD

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Reference
Elements of x-ray diffraction by B.D. Cullity

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