Treść książki

Przejdź do opcji czytnikaPrzejdź do nawigacjiPrzejdź do informacjiPrzejdź do stopki
22
1.AnIntroductiontotheCrystalStructuresofOxidePerovskites
in[5]noevidenceforthedisorderwasfound.Ontheotherhand,Senn[11]
recentlydecidedthatthedisorderwaspresent.Agoodpaperinwhichthis
topicisreviewedisgivenin[12].AnicerecentpaperbyShaoandZuo[13]
usingconvergentbeamelectrondifractionhasconfirmedthatinreality
inthetetragonalphasetherearelargeregionsshowinganormaltetragonal
structuremixedwithsymmetry-breakingregions.Inthispicture,thetrue
structureofBaTiO
3inthisphaseisactuallyamixtureoforderedanddisor-
deredregions.Theimportantthingtonoteisthatthiswasthefirstevidence
thatinferroelectricperovskites,attentionneedstobepaidnotonlytothe
averagecrystalstructurebutalsotowhathappensatthelocalscalebelow
thecoherencelengthoftheradiationused(e.g.forx-ray,neutronandelec-
trondifraction).Interestingly,theperovskitePbTiO
3isisostructuralwith
tetragonalBaTiO
3,yetthereisnoevidenceofpatterneddifusescattering,
anditshigh-temperaturephasetransitiontothecubicphaseappearstobe
simplygivenbyanunderdampedsoftmode.
Whereasintheearlydays,perovskitecrystalstructuresweretreated
purelyintermsoftranslationalperiodicity,theinclusionoflargeregions
ofdisorderisnowbeingfoundtobeofincreasingimportance.Forinstance,
considerthestructuresoftheimportantceramicpiezoelectricPbZr
1-xTi
xO
3
(PZT).ThephasediagramshowsthatontheZr-richsideofthephasedi-
agramtheaveragesymmetryofthecrystallitesisR3morR3c,depending
oncomposition.Forx=0.48thereisasuddenchangetotetragonalP4mm
symmetry:theboundaryhereisknownastheMorphotropicPhaseBound-
ary(MPB).ItisattheMPBthatthepiezoelectricactivityishighest,and
overthelast50yearsorsomanyattemptshavebeenmadetounderstand
this.
Inrecenttimes,Nohedaetal.[14]showedthatontheZr-richsideofthe
MPBforanarrowcompositionrangethestructureisactuallymonoclinic.
However,thereappearstobenobordertotherhombohedralphases.This
problemhasrecentlybeensolvedinreference[15]whereitwasshown
thatontherhombohedralsidethesymmetryoftheunitcellsismonoclinic
butwiththecellsarrangedinarandomorientationinsomeregionsofthe
crystalwithembeddedorderedmonoclinicregions(Figure1.8).Whenav-
eragedoverallunitcells,thecrystalsymmetryappearstoberhombohe-
dral,spacegroupR3morR3c,dependingoncomposition
Takenasawholetheaveragestructurethenlooksrhombohedral.Asthe
compositionchangestowardstheMPBtheorderedmonoclinicregions
growattheexpenseofthedisorderedregionsuntiltheyaresumciently
largetobeseenasadistinctmonoclinicphase.Theimportanceofthe
monoclinicregionsisthatthePbpolardisplacementslieonasinglemirror