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DefectsinCrystal

Basedondimensionality PointDefects0D LineDefects/Dislocations1 D Line Defects/ Dislocations 1D SurfaceDefects/Plane2D BulkDefects/volume3D

Oneortwoatomicdiametersisthetypicalsize. Vacancy:atomicsitefromwheretheatomismissing. y g SymbolV Substitutional impurity:Foreignatomthatsubstituteor replacesaparentatominthecrystal. Example:AlandPdopedinSilicon. Interstitialimpurity:smallsizedatomoccupyingthevoid spaceintheparentcrystal. Inclosedpackedstructures,thelargestatomthatcanfit theoctahedralandtetrahedralvoidshaveradii0.414rand 0.225r,respectively,whereristheradiusoftheparent atom.

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>whenanionis replacedbyforeignionthe parentionsitsinthe interstitialposition. >whenapairofcation andanionismissing and anion is missing Inionicdefectsoverall electricalneutralityshould bemaintained.

KrogerVink Notation:

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Schottky Defect:Missingcations andanionsin theratioofthechemicalformula,i.e.inMgO th ti f th h i l f l i i M O

Frenkel Defect:Vacancy+Interstitial,i.e.in CaF2

Compositionofanioniccrystaldoesnotcorrespondto theexactstoichiometricformula.Suchdefect structureshaveappreciableconcentrationsofpoint structures have appreciable concentrations of point defects.

Excesscation occupyinterstitialvoids.M1+xO Vacantcation sitesarepresentM1xO OxygenvacanciesarepresentMO1x ExcessoxygenisthereMO1+x:thisisusuallynotthecaseastheanionsareusually biggerinsizethancations sotheycantsitinthevoids.

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Incaseofacrystalwithdefectweshouldnote thefollowing: the following: MassBalance:Cantcreateordestroymatterin reactiontoformdefect ChargeBalance:Cantcreateordestroymatterin reactiontoformdefect reaction to form defect SiteBalance:Sitesmustappearincorrectratiofor stoichiometriccrystaloneithersideofreaction

G(n) = nH nTS N = number of defects

G(n) G( )

G=nHf kT[Nln N(Nn)ln (Nn)nln n]

max

Thefreeenergycurvewillshowminimaat equilibriumstateofcrystal Togetequilibriumconcentrationweset

min

So the equilibrium concentration would be

Fromthiscurveweseethatforfreeenergytobeminimumtherehastobecertain concentrationofpointdefects.Thuspointdefectscomenaturallyinmaterials.

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SignificanceofDefects
Dopants areintentionallyaddedimpurities(tomakealloys oraffectchangesinproperties).Alloyformationmostlikely whendopant anionsandcations arecloseinsizetooriginal h d i d i l i i i i l material. Isovalent dopants:substitutionspecieshavethesame charge.
NaCl:AgCl Na1xAgxCl(alloyoncation site) AgBr:AgCl AgBr1xClx (alloyonanionsite)

Aleovalent dopant:substitutionspecieshasdifferent p p charge.

NaCl:CaCl2couldbeeitherNa12xCax xCl orNa1xCaxClClxi eithercouldhappen;experimentally,firstisfound.

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DislocationsorLineDefects.
dislocationsarelinedefects;insteadof thelossofatoms(aswithpointdefects), theycanbelookedatasanextrapartial lineorplaneofatoms. line or plane of atoms lookslikeaperfectcrystal,butifyoulook atthefigurefromalowangle,youseean extrapartialline.

Dislocationcanbeoftwo types: Edgedislocation ScrewDislocation

Burgersvectortodefinedislocation
Waytodescribedislocation.
4 33 33 4 4 4

Above:Burgerscircuitfordislocationfreematerial.

notecompressedbondsandelongatedbonds.

ToRight:Dosamewithdislocationandenduppaststartingpoint. Vectorb=distancetogetbacktocircuit.

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ScrewDislocations

bisparallel

PartialDislocations

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