Nanomaterial crystallinity

GoalsofTodaysLecture
Provideaquickoverviewofthecrystallineandamorphousmaterials
Discusscrystallinity ofnanomaterials
DemonstratetheapplicabilityofBraggsLawfornanomaterials
empiricalformula
Compatibilityfornanomaterials
Discussthebehaviorofdiffractionpattern
Brieflymentionthedataanalysis
Understandingrawdata
indexing
Crystallitesizeanalysis
Discussotherwaystoevaluatecrystallitesize

Assumptions:youdonotunderstandthebasicsofcrystallography,Xraydiffraction,
andtheoperationofaBraggBrentanodiffractometer
 Understandingcrystallineandamorphoussolids

Acrystalisaregular,repeatingarrangementofatomsormolecules.Themajorityofsolids,
includingallmetals,adoptacrystallinearrangementbecausetheamountofstabilization
achievedbyanchoringinteractionsbetweenneighboring particlesisatitsgreatestwhen
theparticlesadoptregular(ratherthanrandom)arrangements.
Inthecrystallinearrangement,theparticlespackefficientlytogethertominimizethe
totalintermolecularenergy

Crystallinity ofnanomaterials

Controlled synthesis at atomic scale precision resulting in higher order of crystallinity

Particularcrystalstructureisformed

Explainingthecrystalplane

Theunitcellisthebasicrepeating
unitthatdefinesacrystal.
Parallelplanesofatoms
intersectingtheunitcellareused
todefinedirectionsanddistances
inthecrystal.
Thesecrystallographicplanes
areidentifiedbyMillerindices.
 Theatomsinacrystalareaperiodicarrayofcoherent
scatterers andthuscandiffractlight.
Diffractionoccurswheneachobjectinaperiodicarrayscattersradiation
coherently,producingconcertedconstructiveinterference atspecific
angles.
Theelectrons inanatomcoherentlyscatterlight.
Theelectronsinteractwiththeoscillatingelectricfieldofthelight
wave.
Atomsinacrystalformaperiodicarrayofcoherentscatterers.
ThewavelengthofXraysaresimilartothedistancebetweenatoms.
Diffractionfromdifferentplanesofatomsproducesadiffraction
pattern,whichcontainsinformationabouttheatomicarrangement
withinthecrystal
XRaysarealsoreflected,scatteredincoherently,absorbed,refracted,and
transmittedwhentheyinteractwithmatter.
 I) Introduction

WavelengthsforXRadiationareSometimesUpdated
Copper Bearden Holzer et al. Cobalt Bearden Holzer et al.
Anodes (1967) (1997) Anodes (1967) (1997)
Cu K1 1.54056 1.540598 Co K1 1.788965 1.789010
Cu K2 1.54439 1.544426 Co K2 1.792850 1.792900
Cu K 1.39220 1.392250 Co K 1.62079 1.620830

Molybdenum Chromium
Anodes Anodes
Mo K1 0.709300 0.709319 Cr K1 2.28970 2.289760

Mo K2 0.713590 0.713609 Cr K2 2.293606 2.293663

Mo K 0.632288 0.632305 Cr K 2.08487 2.084920

OftenquotedvaluesfromCullity (1956)andBearden,Rev.Mod.Phys.39 (1967)

areincorrect.
ValuesfromBearden(1967)arereprintedininternationalTablesforXRay
Crystallography andmostXRDtextbooks.
MostrecentvaluesarefromHlzer etal.Phys.Rev.A 56 (1997)
HasyourXRDanalysissoftwarebeenupdated?
 Ourpowderdiffractometers typicallyusetheBragg
Brentanogeometry.

Detector
X-ray
tube

Theincidentangle,w,isdefinedbetweentheXraysourceandthesample.
Thediffractedangle,2q,isdefinedbetweentheincidentbeamandthedetector
angle.
Theincidentanglewisalways ofthedetectorangle2q.
Inaq:2qinstrument(e.g.Rigaku RU300),thetubeisfixed,thesamplerotatesatq
/minandthedetectorrotatesat2q/min.
Inaq:q instrument(e.g.PANalytical XPert Pro),thesampleisfixedandthetube
rotatesatarateq/minandthedetectorrotatesatarateofq/min.

AsinglecrystalspecimeninaBraggBrentanodiffractometer wouldproduce
onlyonefamilyofpeaksinthediffractionpattern.

At 20.6 2, Braggs law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, 2; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is d100, they appear at
(the perpendicular to those planes does 42 2.
not bisect the incident and diffracted
beams). Only background is observed.
 Apolycrystallinesampleshouldcontainthousandsofcrystallites.
Therefore,allpossiblediffractionpeaksshouldbeobserved.

2 2 2

Foreverysetofplanes,therewillbeasmallpercentageofcrystallitesthatareproperlyoriented
todiffract(theplaneperpendicularbisectstheincidentanddiffractedbeams).
Basicassumptionsofpowderdiffractionarethatforeverysetofplanesthereisanequal
numberofcrystallitesthatwilldiffractandthatthereisastatisticallyrelevantnumberof
crystallites,notjustoneortwo.

PowderDiffractionismoreaptlynamedpolycrystallinediffraction
Samplescanbepowder,sinteredpellets,coatingsonsubstrates,
engineblocks,
Ifthecrystallitesarerandomlyoriented,andthereareenoughofthem,
thentheywillproduceacontinuousDebye cone.
Inalineardiffractionpattern,thedetectorscansthroughanarcthat
intersectseachDebye coneatasinglepoint;thusgivingtheappearanceof
adiscretediffractionpeak.
 PATTERNWITHFIXEDDETECTOR

Diffractionpatternsarebestreportedusingdhkl andrelative
intensityratherthan2 andabsoluteintensity.

Thepeakpositionas2 dependsoninstrumentalcharacteristicssuchas
wavelength.
Thepeakpositionasdhkl isanintrinsic,instrumentindependent,
materialproperty.
BraggsLawisusedtoconvertobserved2 positionstodhkl.
Theabsoluteintensity,i.e.thenumberofXraysobservedinagivenpeak,
canvaryduetoinstrumentalandexperimentalparameters.
Therelativeintensitiesofthediffractionpeaksshouldbeinstrument
independent.
Tocalculaterelativeintensity,dividetheabsoluteintensityof
everypeakbytheabsoluteintensityofthemostintensepeak,and
thenconverttoapercentage.Themostintensepeakofaphaseis
thereforealwayscalledthe100%peak.
Peakareasaremuchmorereliablethanpeakheightsasameasure of
intensity.
 Powderdiffractiondataconsistsofarecordofphotonintensity
versusdetectorangle2q.
Diffractiondatacanbereducedtoalistofpeakpositionsandintensities
Eachdhkl correspondstoafamily ofatomicplanes{hkl}
individualplanescannotberesolved thisisalimitationofpowderdiffractionversus
singlecrystaldiffraction
Raw Data Reduced dI list
Position Intensity
[2q] [cts] hkl dhkl () Relative
Intensity
25.2000 372.0000
(%)
25.2400 460.0000
25.2800 576.0000
{012} 3.4935 49.8

25.3200 752.0000 {104} 2.5583 85.8

25.3600 1088.0000
25.4000 1488.0000 {110} 2.3852 36.1
25.4400 1892.0000
{006} 2.1701 1.9
25.4800 2104.0000
25.5200 1720.0000 {113} 2.0903 100.0
25.5600 1216.0000
{202} 1.9680 1.4
25.6000 732.0000
25.6400 456.0000
25.6800 380.0000
25.7200 328.0000
 CRYSTALLITESIZEBROADENING
K
B(2 ) =
L cos
PeakWidthduetocrystallitesizevariesinverselywithcrystallitesize
asthecrystallitesizegetssmaller,thepeakgetsbroader
Thepeakwidthvarieswith2 ascos
Thecrystallitesizebroadeningismostpronouncedatlargeangles2
However,theinstrumentalprofilewidthandmicrostrain broadening
arealsolargestatlargeangles2
peakintensityisusuallyweakestatlargerangles2
Ifusingasinglepeak,oftengetbetterresultsfromusingdiffractionpeaks
between30and50o 2
below30o 2,peakasymmetrycompromisesprofileanalysis
 TheScherrer Constant,K
K 0.94
B(2 ) = B(2 ) =
L cos L cos
Theconstantofproportionality,K(theScherrer constant)dependsonthehow
thewidthisdetermined,theshapeofthecrystal,andthesizedistribution
themostcommonvaluesforKare:
0.94forFWHMofsphericalcrystalswithcubicsymmetry
0.89forintegralbreadthofsphericalcrystalsw/cubicsymmetry
1,because0.94and0.89bothroundupto1
Kactuallyvariesfrom0.62to2.08
ForanexcellentdiscussionofK,refertoJILangfordandAJCWilson,Scherrer
aftersixtyyears:Asurveyandsomenewresultsinthedeterminationof
crystallitesize, J.Appl.Cryst. 11 (1978)p102113.

REMEMBER,CRYSTALLITESIZEISDIFFERENTTHAN
PARTICLESIZE
Aparticlemaybemadeupofseveraldifferentcrystallites
Crystallitesizeoftenmatchesgrainsize,butthereareexceptions
 Crystallite Shape
Thoughtheshapeofcrystallitesisusuallyirregular,wecanoften
approximatethemas:
sphere,cube,tetrahedra,oroctahedra
parallelepipedssuchasneedlesorplates
prismsorcylinders
MostapplicationsofScherrer analysisassumesphericalcrystalliteshapes
Ifweknowtheaveragecrystalliteshapefromanotheranalysis,wecan
selectthepropervaluefortheScherrer constantK

Anistropic peakshapescanbeidentifiedbyanistropic peakbroadening

ifthedimensionsofacrystalliteare2x*2y*200z,then(h00)and
(0k0)peakswillbemorebroadenedthen(00l)peaks.

YoucanuseXRDtodetermine
PhaseCompositionofaSample
QuantitativePhaseAnalysis:determinetherelativeamountsof
phasesinamixturebyreferencingtherelativepeakintensities
UnitcelllatticeparametersandBravais latticesymmetry
Indexpeakpositions
Latticeparameterscanvaryasafunctionof,andthereforegive you
informationabout,alloying,doping,solidsolutions,strains,etc.
ResidualStrain(macrostrain)
CrystalStructure
ByRietveld refinementoftheentirediffractionpattern
Epitaxy/Texture/Orientation
CrystalliteSizeandMicrostrain
Indicatedbypeakbroadening
Otherdefects(stackingfaults,etc.)canbemeasuredbyanalysisof
peakshapesandpeakwidth
Wehaveinsitucapabilities,too(evaluateallpropertiesaboveasa
functionoftime,temperature,andgasenvironment)