Structure elucidation from XRD

X-rays are electromagnetic waves with a wavelength in the range of interatomic distances (0.1-10 )

topics
Structure analysis by X-ray diffraction from crystals Crystallography X-ray diffraction from polycrystalline samples (powders); Evaluation of the intensities of X-rays diffracted from polycrystalline samples; Elucidation of simple inorganic crystal structures starting from the model structures and comparison of the intensities calculated for the model structures with the observed intensities;

What is X-ray Diffraction?

Practical aspect
3 basic components of an X-ray diffractometer 1. X-ray source 2. Specimen 3. X-ray detector

1. X-Ray source Generated by directing an electron beam of high voltage at a metal target inside an evacuated x-ray tube Cu K ~ 8.04 keV (=0.154184 nm) is the most used metal target due to its high intensity

2. Specimen Quantity ~ a few mg Grain size 50m (passed 325 mesh sieve) Applied as a thin layer of powder/film onto a nondiffracting material, such as microscope glass slide

3. Detector 3 main types: proportional, scintillation, and solid-state The most used is proportional

Solid matter crystalline

The atoms are arranged in a regular pattern, and there is as smallest volume element that by repetition in three dimensions describes the crystal (a unit cell). Long range order (>103 molecules)

non-crystalline (amorphous)
The atoms and molecules are arranged in a random way similar to the disorder we find in a liquid do not form crystallites. Glasses are amorphous materials. Small particles with no long-range order (100 )
Intensity (a.u)

B
A [101] A A A A

5h Am 4h 3h 2h

single crystal
Solid which contains single crystallite

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polycrystalline
Solids which contain many small, randomly oriented and joined crystallites/grains

2 ( )
o

Single crystal long-range order

polycrystalline consists of some single crystal region (grains) separated by grain boundaries

amorphous not ordered short-range order

Polymers can also present ordered region as in crystalline materials, called crystallite

crystallite region

amorphous region

XRD can be used to provide information about the structure of amorphous or non-crystalline materials, such as glass

constructive interference results in diffraction line, but destructive interference does not

monochromatic/single wavelength with highest intensity is used as the X-ray source

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 In powder or polycrystalline diffraction it is important to have a sample with a smooth plane surface. If possible, grind the sample down to particles of about 0.002 mm to 0.005 mm cross section. The ideal sample is homogeneous and the crystallites are randomly distributed random distribution of all possible h,k,l planes The sample is pressed into a sample holder so that we have a smooth flat surface.

Only crystallites having reflecting planes (h,k, l) parallel to the specimen surface will contribute to the reflected intensities. If we have a truly random sample, each possible reflection from a given set of h, k, l planes an equal number of crystallites contributing to it. We only have to rock the sample through the glancing angle THETA in order to produce all possible reflections.

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X-ray Diffraction Pattern

Consists of a series of peaks The peak intensity as the ordinate (y axis) expressed as an arbitrary units The measured diffraction angle, 2, along the abscissa The as-recorded XRD pattern generally have a background, then it is usually substracted and the peaks smoothened Sources information: Powder Diffraction File (PDF) JCPDS (database of standard XRD pattern by International Centre for Diffraction Data)

Crystallography: reviews

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About 95% of all solid materials can be described as crystalline When X-rays interact with a crystalline substance (phase) gets a diffraction pattern In 1919 A.W.Hull gave a paper titled, A New Method of Chemical Analysis. Here he pointed out that .every crystalline substance gives a pattern; the same substance always gives the same pattern; and in a mixture of substances each produces its pattern independently of the others. The X-ray diffraction pattern of a pure substance a fingerprint finger print identification

The powder diffraction method is thus ideally suited for characterization and identification of crystalline/polycrystalline phases

Today about 50,000 inorganic and 25,000 organic single component, crystalline phases, diffraction patterns have been collected and stored on magnetic or optical media as standards The main use of powder diffraction is to identify components in a sample by a search/match procedure The areas under the peak are related to the amount of each phase present in the sample For single-phase materials the crystal structure can be obtained directly using X-Ray diffraction (XRD) XRD can be used : for phase identification (With the help of a database of known structures) to determine crystal size, strain and preferred orientation of polycrystalline materials the related technique of X-ray reflection enables accurate determination of film thickness

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Structure analysis by X-ray diffraction from crystals

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XRD patterns of furnace materials and reference patterns of identified phases

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TiO2 with fully anatase (A) as the crystalline phase

Applications: Identification of crystalline phases

TiO2 has 3 major crystalline phases, anatase (A), rutile (R) and brookite (B) with fully anatase (A) as the crystalline phase

A A A A

TiO2 with anatase (A) and rutile (R) as the crystalline phases

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Peak intensities
Evaluation of the intensities of X-rays diffracted from polycrystalline samples evaluating crystallinity

taking the sum total of relative intensities of ten individual characteristic peaks1 then taking the ratio over the corresponding relative intensities of standard materials E.g.: Comparing crystallinity of flyash-based zeolite-A using XRD and IR spectroscopy
1CURRENT

SCIENCE, VOL. 89, NO. 12, 25 DECEMBER 2005

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% crystallinity = (IR sample)/(IR standard)

% crystallinity = (AD4R)/(ATO4)

72.8%

85%

98.6% 98.6%

98.6%

100%

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83.2% 72.8%

92%

96.2%

93.3%

100%

Crystallinity = (A ratio of 560 over 464 cm-1 bands of sample/reference) x 100%

D=

K cos

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Applications: Determination of Crystal Size

Scherrer equation: Bcrystallites = (k)/(L cos )
k constant ~ 1 (precision error 10%) L average crystal size (nm) wavelength of the X-rays used (nm) Bragg angle (radians) B full width at half maximum (FWHM, radians)
Cu = 0.15406 nm L1 = 0.0061 1=25.28 B1 = 25.3 nm L2 = 0.0061 2=37.8 B2 = 25.26 nm

Example: anatase TiO2

Different crystallite sizes

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determination and refinement of lattice parameters (indexing)

relationship between Miller indices and diffraction angles

sin 2 =

2
4a

(h 2 + k 2 + l 2 ) 2

sin 2 = C (h 2 + k 2 + l 2 )

dividing the above equation with the first reflection angle gives the ratio of hkl

sin 2 (h 2 + k 2 + l 2 ) = sin 2 1 (h12 + k12 + l12 )

the ratio of hkl define the possible Miller indices: ratio = h2 + k2 + l2 if there are some possible hkl, the highest number comes first After indexing, one of the peaks can be used to calculate the cell parameters. As the error in measuring the diffraction angles is a systematic error, the last reflection data will be used

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exercise 1: indexing XRD data (cubic)

2 19.213 27.302 33.602 38.995 43.830 48.266 56.331 60.093 63.705 67.213 70.634 sin2 0.0279 ratio 1 Miller indices 100
1. define the Miller indices 2. calculate the lattice parameters

lattice type and systematic absences on cubic system

destructive interferences occurring between the diffracted waves intensity cancels out eg:

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 For example MoO3 crystallizes in thin plates (like sheets of paper) these crystals will pack with the flat surfaces in a parallel orientation. Comparing the intensity between a randomly oriented diffraction pattern and a preferred oriented diffraction pattern can look entirely different. Quantitative analysis depend on intensity ratios which are greatly distorted by preferred orientation. Careful sample preparation is most important to deal with preferred orientation samples The following illustrations show the Mo O3 spectra's collected by using transmission , Debye-Scherrer capillary and reflection mode.

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TiO2 film layered on SnO2 (S) thin film with anatase (A) as the crystalline phases

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ZnO nanorod

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