N3C1-5 Ivan Khodyuk IEEE NSS 2015

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.


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


Outline

q  IntroducHono  Globaltrendsinradia=ondetec=onmaterials


o  Parameterspaceforscin=llatorsR&Dq  Toolstosearchthroughtheparameterspace


q  NaIperformanceengineeringo  Experimentaldesigno  Dataanalysisandresultverifica=ono  Bridgmancrystalgrowtho  NaI:TECcharacteriza=on

q  Conclusionandfuturework


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:


Discoveryofnewmaterial

Binary

Ternary

Quaternary

GlobaltrendinmaterialsforradiaHondetecHon

Time

Numberofelementsinthehost

NaI, CsI

LSO, YAG

GYAG, CLYC

Moreandmoresystemswithcomplexhostsareintroducedasscin=llators

SameorsimilartrendcanbeseeninscinHllators,semiconductors,phosphors…


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


Trendinmaterialsdiscovery

Sta=s=calanalysisof500+scin=llatormaterialsfromscinHllator.lbl.gov

NumberofcomposiHonsgrownasapowerlawofnumberofelements

PublicaHonyear1960 2015

102

103

104

105

Nofp

ossiblecompo

siHo

ns


Example1-MixedcaHons


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


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


From50,000to~90,000ph/MeV

From>5%to~3%at662keV


ImprovementofexisHngmaterials

Developmenthasbeendonebydifferentmeans:

Crystalgrowth• CondiHons• Techniques

ControlofimpuriHes• Rawmaterials• Synthesis

Defectengineering• Bandgap• Co-doping

Forexampleco-dopingwassuccessfullyusedtotargetspecificproperHes

Wekeepthelacceandtrytoimproveperformance

Globalapproach:


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)


IdealscinHllatorsdiscoveryandimprovement

Lapce

• ElementalcomposiHon• Stoichiometry• EnhanceddefectformaHon

Dopants

• DopanttypeandconcentraHon• Co-dopant1typeandconcentraHon• Co-dopant2…

Synthesis

• SynthesistechniqueandcondiHons• Purityofraw• IniHalreactants

EvenwithverygoodguidancewehavefromphysicsandcrystalgrowthitisessenHaltohaveeffecHvetoolstosearchthroughtheparameterspace

EnergyResoluHon

LightOutput

MechanicalproperHes

DecayHme

Price

SelfAbsorpHon

ParameterspaceisexpandingdrasHcallywhenweaccountforallpossiblecombinaHons


Outline

q  IntroducHono  GlobaltrendsinradiaHondetecHonmaterials


o  ParameterspaceforscinHllatorsR&Dq Toolstosearchthroughtheparameterspace


q  NaIperformanceengineeringo  Experimentaldesigno  DataanalysisandresultverificaHono  Bridgmancrystalgrowtho  NaI:TECcharacterizaHon



Combinatorialchemistry

Veryefficientforpowdersandthinfilmswhenprobingluminescent

proper=es

BiSrCaCuOx

DescripHonCombinatorialchemistry-allthepossiblecombina=onsintheparameterspaceareprobedRequirementsPossibilityofsimultaneoussynthesisDesiredproper=esofthematerialscanbeautoma=callytested


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%


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:


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


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


Complementaryspaceprobing

Projection of all 9 points on YZ plain

Orthogonalarraybasedexperimentaldesignrequiresthefewestnumberofexperimentstoprobefullcombinatorialspace

KnotsarearrangedtoformcompleteprojecHononallplanes:XY,XZ,YZ


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


Outline



o  ParameterspaceforscinHllatorsR&Dq  Toolstosearchthroughtheparameterspace

o  Combinatorialchemistryo  Fullfactorialdesigno  FracHonalfactorialdesigno  Responsesurfacemethodology

q NaIperformanceengineeringo  Experimentaldesigno  Dataanalysisandresultverifica=ono  Bridgmancrystalgrowtho  NaI:TECcharacteriza=on



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


SynthesisandcharacterizaHon

Workflow

DesignofExperiment

Selectedcrystalgrowth

Pulse-heightcharacteriza=onDataanalysis

ForeverycomposiHon3-5singlecrystallinepiecesof3x3x3mm3weremeasured


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


Experimentaldesignoutput

ProjecHonsof4dimensionalparametricspaceonsurface:

Zoneofinterest

MulH-regressionanalysisisnecessarytoesHmateopHmalconcentraHons


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:


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


NaI:TECwithcorrectedTlconcentraHon

NaIwithlowerconcentra=onofTl+–0.1mole%inthemeltwasgrownusingthesameBridgmantechnique

52000ph/MeV4.9%at662keV

NaI:TEC(Tl,Eu,Ca)–with52,000ph/MeVand4.9%resoluHonat662keV


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


EnergytransferfromTl+toEu2+

6sà6p

4fà5d

Tl+

Eu2+

[Eu2++Vac]

Tl+


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


Outline



o  ParameterspaceforscinHllatorsR&Dq  Toolstosearchthroughtheparameterspace

o  Combinatorialchemistryo  Fullfactorialdesigno  FracHonalfactorialdesigno  Responsesurfacemethodology

q  NaIperformanceengineeringo  Experimentaldesigno  DataanalysisandresultverificaHono  Bridgmancrystalgrowtho  NaI:TECcharacterizaHon

q Conclusionandfuturework


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


Futurework

Formulavalida=on Scalingup Industrial

verifica=on

NaI:TEC–Canweget2x2incheswithER<5?

Methodologyimprovement

Goalsbroadening

Materialsdiversifica=on

Experimentaldesign


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!

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N3C1-5 Ivan Khodyuk IEEE NSS 2015