n3c1-5 ivan khodyuk ieee nss 2015
TRANSCRIPT
1 IEEENSS2015SanDiego
CombinatorialApproachtoBulkDetectorMaterialEngineering
I.V.Khodyuk,D.Perrodin,S.E.Derenzo,E.D.Bourret,G.A.BizarriLawrenceBerkeleyNa@onalLaboratory,Berkeley,CA-USA
CombinatorialandhighthroughputmaterialsynthesispartofthisworkwassupportedbytheUSDepartmentofHomelandSecurity/DNDOandcrystalgrowth effort by the US Department of Energy/NNSA/DNN R&D and carried out at Lawrence Berkeley Na=onal Laboratory under Contract no.AC02-05CH11231.Thisworkdoesnotcons=tuteanexpressorimpliedendorsementonthepartofthegovernment.
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Outline
q IntroducHono Globaltrendsinradia=ondetec=onmaterials
§ Complexhosts§ Co-doping
o Parameterspaceforscin=llatorsR&Dq Toolstosearchthroughtheparameterspace
o Combinatorialchemistryo Fullfactorialdesigno Frac=onalfactorialdesigno Responsesurfacemethodology
q NaIperformanceengineeringo Experimentaldesigno Dataanalysisandresultverifica=ono Bridgmancrystalgrowtho NaI:TECcharacteriza=on
q Conclusionandfuturework
3 IEEENSS2015SanDiego
Outline
q IntroducHono Globaltrendsinradia=ondetec=onmaterials
§ Complexhosts§ Co-doping
o Parameterspaceforscin=llatorsR&Dq Toolstosearchthroughtheparameterspace
o Combinatorialchemistryo Fullfactorialdesigno Frac=onalfactorialdesigno Responsesurfacemethodology
q NaIperformanceengineeringo Experimentaldesigno Dataanalysisandresultverifica=ono Bridgmancrystalgrowtho NaI:TECcharacteriza=on
q Conclusionandfuturework
4 IEEENSS2015SanDiego
ApplicaHondrivenresearch
Howcanweenhancespectroscopiccapabili=esof“lowcost”scin=llators?
Isitpossibletodecreasepriceofexis=ng“advanced”materials?
RealworldapplicaHonsarethemaindrivingforcesbehindradiaHonmaterialsdiscoveryanddevelopment
NaI:TlCsI:Tl,Na
BeYerEnergyresolu=on
Isotopediscrimina=on
LaBr3:CeSrI2:Eu
Lowerprice Moreapplica=ons
DiscovernewmaterialsorImprovealreadyexisHng
Homelandsecurity:
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Discoveryofnewmaterial
Binary
Ternary
Quaternary
GlobaltrendinmaterialsforradiaHondetecHon
Time
Numberofelementsinthehost
NaI, CsI
LSO, YAG
GYAG, CLYC
Moreandmoresystemswithcomplexhostsareintroducedasscin=llators
SameorsimilartrendcanbeseeninscinHllators,semiconductors,phosphors…
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MixedmaterialsperformbeRerLuminosity
,arb.u
n.
Cs(Br,I) (La,Ce)F3 La(Cl,Br)3
(Lu,Y)AP (Lu,Gd)SO Gd(Al,Ga)G
Y(Al,Ga)G (Zn,Mg)WO (Ca,Sr)S
From:GekHn,A.V.;Belsky,A.N.;Vasil'ev,A.N.,"ScinHllaHonEfficiencyImprovementbyMixedCrystalUse,"inNuclearScience,IEEETransac1onson,vol.61,no.1,pp.262-270,Feb.2014
InmanycasescomplexhostsleadtobeRerscinHllaHonperformance
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Trendinmaterialsdiscovery
Sta=s=calanalysisof500+scin=llatormaterialsfromscinHllator.lbl.gov
NumberofcomposiHonsgrownasapowerlawofnumberofelements
PublicaHonyear1960 2015
102
103
104
105
Nofp
ossiblecompo
siHo
ns
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Example1-MixedcaHons
PublicaHonyear1960 2015
Gd3Al5O12
(Gd,Y)3Al5O12
(Gd,Y)3(Ga,Al)5O12
Dorenbos,P.etal.,Rad.Eff.Def.inSol.,p.135,1995 Cherepy,N.Jetal,IEEETNS56(3)p.873,2009
K.Kamadaetal.,CrystalGrowth&Design,11,p.4484,2011
Significantimprovementoflightoutputinmixedca=onssystems
From10,000to60,000ph/MeV
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CsI
CsBa2I5
BaBr2
BaBrI
J.BonanomiandJ.Rossel,Helv.Phys.Acta.,vol.25,p.725,1952.
E.D.Bourret-Courchesneetal.,NIMA,612:138,2009.
J.Sellingetal.,J.ofAppl.Phys.,101:034901,2007.
E.D.Bourret-Courchesne,NIMA,613:95,2010.
Example1-Mixedanions
SignificantimprovementofenergyresoluHonandlightoutput
PublicaHonyear1960 2015
From50,000to~90,000ph/MeV
From>5%to~3%at662keV
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ImprovementofexisHngmaterials
Developmenthasbeendonebydifferentmeans:
Crystalgrowth• CondiHons• Techniques
ControlofimpuriHes• Rawmaterials• Synthesis
Defectengineering• Bandgap• Co-doping
Forexampleco-dopingwassuccessfullyusedtotargetspecificproperHes
Wekeepthelacceandtrytoimproveperformance
Globalapproach:
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Targetedimprovementbyco-doping
Mechanicalproper=eswereaddressedby
aliovalentco-doping:Sr,Ca,Ba,Mg
Improvedscin=lla=onperformancehasbeendiscovered:Ba,Sr,Ca
RecordEnergyResolu=on
ImprovedMechanicalproper=es
LSO:Ce Ca Decay time
Light Output
PbWO4 LaTraps
removalDecay=me
ThereareafewexampleswhenspecificproperHesofexisHngmaterialshavebeenimprovedbyco-dopingwithasmallamountofop1callypassiveelements
Zoominexample:LaBr3:CeandCeBr3
SignificantimprovementofscinHllaHonandmechanicalproperHeshasbeenachievedbyco-dopingwithfewhundredppmofSr2+
Harrison,M.J.etal.,IEEETNS56(3)2009 Yang,K.etal.,IEEENSS/MIC2012N1-135 Alekhin,M.S.Appl.Phys.LeR.102,161915(2013)
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IdealscinHllatorsdiscoveryandimprovement
Lapce
• ElementalcomposiHon• Stoichiometry• EnhanceddefectformaHon
Dopants
• DopanttypeandconcentraHon• Co-dopant1typeandconcentraHon• Co-dopant2…
Synthesis
• SynthesistechniqueandcondiHons• Purityofraw• IniHalreactants
EvenwithverygoodguidancewehavefromphysicsandcrystalgrowthitisessenHaltohaveeffecHvetoolstosearchthroughtheparameterspace
EnergyResoluHon
LightOutput
MechanicalproperHes
DecayHme
Price
SelfAbsorpHon
ParameterspaceisexpandingdrasHcallywhenweaccountforallpossiblecombinaHons
13 IEEENSS2015SanDiego
Outline
q IntroducHono GlobaltrendsinradiaHondetecHonmaterials
§ Complexhosts§ Co-doping
o ParameterspaceforscinHllatorsR&Dq Toolstosearchthroughtheparameterspace
o Combinatorialchemistryo Fullfactorialdesigno Frac=onalfactorialdesigno Responsesurfacemethodology
q NaIperformanceengineeringo Experimentaldesigno DataanalysisandresultverificaHono Bridgmancrystalgrowtho NaI:TECcharacterizaHon
q Conclusionandfuturework
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Combinatorialchemistry
Veryefficientforpowdersandthinfilmswhenprobingluminescent
proper=es
BiSrCaCuOx
DescripHonCombinatorialchemistry-allthepossiblecombina=onsintheparameterspaceareprobedRequirementsPossibilityofsimultaneoussynthesisDesiredproper=esofthematerialscanbeautoma=callytested
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CombinatorialchemistryandscinHllator?
• Cannot use powder/thin film • Need single crystal of representative quality
Requirement to access scintillation properties: Gamma response and photopeak for energy resolution and light output
The speed of the approach is as fast as the slowest part of the process.
Numerous possibility Extremely time
consuming
Not applicable!
Crystal growth/ Material Synthesis
A = Li, Na, K, Cs X = F, Cl, Br, I Y = 0.01, 0.05, 0.1, 0.2
54 = 625 crystals
Cs2ALa1-yCeyX6:IIA
5factorsx4levels Fullfactorialdesign
IIA = Mg, Ca, Sr, Ba [IIA] = 0.05%, 0.1%, 0.25%, 0.5%
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FromFULLtoFRACTIONALfactorialdesign
F2
F3
F1
Can we search through the parameter space more efficiently?
Cs2ALa1-yCeyX6
33 = 27 crystals
3factorsx3levels Fullfactorialdesign
A, X, Y -> factors Li, Na, Cs -> levels of Factor A
A=Li, Na, Cs X=Cl, Br, I Y=0.01, 0.05, 0.1
Example:
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Factor Level 1 Level 2 Level 3 F1 L11 L21 L31
F2 L12 L22 L32
F3 L13 L23 L33
Fractional factorial design 33 using L9 OA
F2
F3
F1
FracHonalfactorialdesign
L9 Orthogonal Array Design F1 F2 F3
1 L11 L12 L13
2 L11 L22 L23
3 L11 L32 L33
4 L21 L12 L23
5 L21 L22 L33
6 L21 L32 L13
7 L31 L12 L33
8 L31 L22 L13
9 L31 L32 L23
33 = 27 9 crystals 54 = 625 16 crystals
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Fractional factorial design 33 using L9 OA
Example:Cs2ALa1-yCeyX6
Orthogonal Experimental Set Design A X Y
1 Li Cl 0.01
2 Li Br 0.05
3 Li I 0.1
4 Na Cl 0.05
5 Na Br 0.1
6 Na I 0.01
7 Cs Cl 0.1
8 Cs Br 0.01
9 Cs I 0.05
Factor Level 1 Level 2 Level 3 A Li Na Cs
X Cl Br I
Y 0.01 0.05 0.1
#1 Cs2LiLaCl6:1%Ce #5 Cs2NaLaBr6:10%Ce #9 Cs3LaI6:5%Ce
X
Y
A
#1
#5
#9
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Complementaryspaceprobing
Projection of all 9 points on YZ plain
Orthogonalarraybasedexperimentaldesignrequiresthefewestnumberofexperimentstoprobefullcombinatorialspace
KnotsarearrangedtoformcompleteprojecHononallplanes:XY,XZ,YZ
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FullspacereconstrucHon
Visualiza=oncanbeusedonlyforfactorsthatcanberepresentedbycon=nuousfunc=on–concentra=on,ra=o,temperature,etc.
Combinatorialtechniqueitselfisnotlimitedtothat!
Byhavingall3projecHonstakenthefullmapofthespacecanbereconstructed
Risk – part of the information can be lost Advantage – minimal N of experiments
21 IEEENSS2015SanDiego
Outline
q IntroducHono GlobaltrendsinradiaHondetecHonmaterials
§ Complexhosts§ Co-doping
o ParameterspaceforscinHllatorsR&Dq Toolstosearchthroughtheparameterspace
o Combinatorialchemistryo Fullfactorialdesigno FracHonalfactorialdesigno Responsesurfacemethodology
q NaIperformanceengineeringo Experimentaldesigno Dataanalysisandresultverifica=ono Bridgmancrystalgrowtho NaI:TECcharacteriza=on
q Conclusionandfuturework
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NaI–Performanceengineering
Factor Level1 Level2 Level3 Level4
Dopant Tl - - -
[Dopant],% 0.0 0.1 0.25 0.5
Co-dopant Mg Ca Sr Ba
[co-dopant] 0.1 0.2 0.4 0.8
[Eu2+],% 1.0 0.5 0.1 0.0
Fullfactorialdesignwouldrequiretrialof256differentcrystalsL16orthogonalarraybasedFracHonalFactorialdesign-only16crystals
Goal:ImprovementofNaIEnergyResoluHonbyco-doping
Benchmark:NaI:Tl–40,000ph/MeVand6.3%at662keVBestvaluereported-Shiranetal.:NaI:Tl,Eu–48,000ph/MeVand6.2%at662keVBestunreportedvalue:NaI:Tl-44,000ph/MeVand5.9%at662keV
Factorial(parametric)spacetodiscover:
Shiran,N.V.etal,IEEETNS57(3)p.1233,2010
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SynthesisandcharacterizaHon
Workflow
DesignofExperiment
Selectedcrystalgrowth
Pulse-heightcharacteriza=onDataanalysis
ForeverycomposiHon3-5singlecrystallinepiecesof3x3x3mm3weremeasured
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DesignofExperimentFracHonalfactorialdesignusingL16orthogonalarray
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 160
5
10
15
20
Homemadereference
C ommerc ia lreference
Ene
rgyRes
olution@
662
keV(%)
D es ignnumber
Mg
C a
S r
B a
B aMg
C a S r
B a
Mg
C a
S r
B aMg
C aS r
S tatis tica llimitfor44000photons /MeV
Noneoftheexperimentalcomposi=onssignificantlyoverperformthereference
InformaHononthedirecHonofimprovementisencodedinthedesign
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Experimentaldesignoutput
ProjecHonsof4dimensionalparametricspaceonsurface:
Zoneofinterest
MulH-regressionanalysisisnecessarytoesHmateopHmalconcentraHons
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OpHmumcomposiHonsynthesis
0 1000 2000 3000 4000 50000
100
200
300
400
Cou
nts
P MT 1C hannel
S 4
L Y = 46200ph/MeV*E R = 5.4%
*LOcorrectedforPMTQENaI:0.25%Tl,0.1%Eu,0.2%Ca
Quickop=malcomposi=onsynthesisandperformanceevalua=on
OpHmalcomposiHonoverperformthebenchmarkreferenceevenwhenweoperateinthenominalconcentraHonsparametricspace
Factor Level1 Level2 Level3 Level4
Dopant Tl - - -
[Dopant],% 0.0 0.1 0.25 0.5
Co-dopant Mg Ca Sr Ba
[co-dopant] 0.1 0.2 0.4 0.8
[Eu2+],% 1.0 0.5 0.1 0.0
Factorialspacetodiscover:
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OpHmumcomposiHoncrystalgrowth
NaI:0.25%Tl+,0.1%Eu2+,0.2%Ca2+–nominalconcentraHonsinthemelt
Partofboule [Tl+],ppmwt
[Ca2+],ppmwt
[Eu2+],ppmwt
nominalinmelt 3470 540 1000top 14641 580 890center 1500 490 940boRom 880 580 940
InducHvelyCoupledPlasmaMassSpectrometry(ICP-MS)results:
42 43 44 45 46 47 48 49 50 51 522.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
topcenterbottom
Ene
rgyRes
olution@
662
keV(%)
L ig htO utput(photons /keV )
5.2% (51.1ph/keV )
S ta tis tica llimitfor44000photons /MeV
R eferenceNa I:T l#0
C ommerc ia lNa I:T l
ThereisasignificantdifferencebetweennominalandrealTlconcentaHonPartsofthecrystalwithlowerTlconcentraHonperformbeRer
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NaI:TECwithcorrectedTlconcentraHon
NaIwithlowerconcentra=onofTl+–0.1mole%inthemeltwasgrownusingthesameBridgmantechnique
52000ph/MeV4.9%at662keV
NaI:TEC(Tl,Eu,Ca)–with52,000ph/MeVand4.9%resoluHonat662keV
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CharacterizaHon:XRLanddecayHme
250 300 350 400 450 500 550 600 650
Na I:T E CNa I:T lre ference
XRLem
ission
intens
ity,a
rb.u
n.
W aveleng th,nm
X-rayluminescence ScinHllaHondecayHme
XRLemissionmaxat450nm 85%ofthelightemiRedthrough“long”1.4μscomponent
0 1000 2000 3000 4000 5000
0.01
0.1
1
τ1 = 240ns -15%
τ2 = 1390ns -85%
Cou
nts/bin
T ime,ns
Na I:T E CNa I:T l
τ = 225ns
backg round
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EnergytransferfromTl+toEu2+
6sà6p
4fà5d
Tl+
Eu2+
[Eu2++Vac]
Tl+
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Tl-Eu energy transfer
maximization
Beneficial defect
creation
Impurity removal
Mechanismsofimprovement
MulHplemechanismsworkinsynergytowardtheimprovementoflightoutputandenergyresoluHon
High Oxygen affinity of Ca and Eu Trapping of carriers
during early stages of scintillation process with subsequent release [Eu2+
Na + VacNa] – hole trap
[Tl0Na + Ca2+Na]
– electron trap
FurtherinvesHgaHonaswellasindustrialverificaHonisrequiredtopushperformanceofNaI:TECevenfurther
32 IEEENSS2015SanDiego
Outline
q IntroducHono GlobaltrendsinradiaHondetecHonmaterials
§ Complexhosts§ Co-doping
o ParameterspaceforscinHllatorsR&Dq Toolstosearchthroughtheparameterspace
o Combinatorialchemistryo Fullfactorialdesigno FracHonalfactorialdesigno Responsesurfacemethodology
q NaIperformanceengineeringo Experimentaldesigno DataanalysisandresultverificaHono Bridgmancrystalgrowtho NaI:TECcharacterizaHon
q Conclusionandfuturework
33 IEEENSS2015SanDiego
Conclusion
• Therearetrendsinradia=ondetec=onmaterialsdiscoveryandimprovementwhichsignificantlyincreasepoten=alcombinatorialspace
• Experimentaldesigntechniquescanbeveryusefultoolstoprobethisspaceinamoreefficientway
• FracHonalfactorialdesignhasbeenusedtospeedupdiscoveryofEu2+andIIAinfluenceonscin=lla=onperformanceofNaI:Tl
• Op=malcomposi=on–NaI:TEC(0.1%Tl+,0.1%Eu2+,0.2%Ca2+)determinedwithmul=-regressionanalysisgives52000photons/MeVand4.9%grownbyBridgman
• NaI:TECunderX-raysandop=calexcita=onisemicnglightpredominantlythroughEu2++Vacclusterwithmaxat450nmandmaindecaycomponentsof240nsand1.4μs
J. Appl. Phys. 118, 084901 (2015); http://dx.doi.org/10.1063/1.4928771
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Futurework
Formulavalida=on Scalingup Industrial
verifica=on
NaI:TEC–Canweget2x2incheswithER<5?
Methodologyimprovement
Goalsbroadening
Materialsdiversifica=on
Experimentaldesign
35 IEEENSS2015SanDiego
AcknowledgementsTheauthorswouldliketothankS.Hanrahan,D.Wilson,M.BoswellandDr.J.PowellfortheirtechnicalandengineeringsupportandDrs.G.Gundiah,M.Gascon,E.SamulonandT.Shalapskafortheirscien=ficinput.CombinatorialandhighthroughputmaterialsynthesispartofthisworkwassupportedbytheUSDepartmentofHomelandSecurity/DNDOandcrystalgrowtheffortbytheUSDepartmentofEnergy/NNSA/DNNR&DandcarriedoutatLawrenceBerkeleyNa=onalLaboratoryunderContractno.AC02-05CH11231.Thisworkdoesnotcons=tuteanexpressorimpliedendorsementonthepartofthegovernment.
Thankyou!