US007977645B1

( 12 ) Ulllted States Patent ( 10) Patent N 0. : US 7, 977, 645 B1

Shah et al. ( 45) Date o f Patent: J u l. 12 , 2 011
64> 2 00711152 512 1: 3 2 2 2 ; 1 ~ ~ ~ ~ ~ ~ 2 5042 512 11
ee er et a . . . . . . . . . . . . . . . . . .
HALIDE SCIN TILLATOR COMPOSITION S 2 003 /0075706 A1 * 4/2 003 Shiang et al. . . . . . . . . . . 2 52 /3 01. 4 R
2 003 /0193 040 A1* 10/2 003 V kat '
( 75) Inv ento rs: Kanai S. Shah, N ewto n, MA ( US) ; ete; " " " " 2 52 /3 014 F
William M. Higgins, Wesbo ro u gh, MA 2 005/0082 484 A1* 4/2 005 Sriv astav a et al. . . . . . . . . 2 50/3 61 R
( Us) . Edgar Van Lo ef Allsto n MA 2 006/02 3 7654 A1* 10/2 006 Sriv astav a 61: 11. . . . . . . . 2 50/3 7011
f 2 007/013 1866 A1* 6/2 007 Sriv astav a 61: 11. . . . . . . . . . . . . 2 50/3 67
ms) J amslaw Glo do Ansto n MA 2 007/013 1874 A1* 6/2 007 Sriv astav a 61: 11. . 2 50/4581
( Us) 2 007/0187608 A1* 8/2 007 Beer et al. . . . . . . . . . . . . . . . . . . . . . 2 50/3 62
2 007/02 8453 4 A1* 12 /2 007 Sriv astav a et al. . . . . . . . 2 50/3 70. 11
( 73 ) Assignee: Radiatio n Mo nito ring Dev ices, Inc. , 2 008/0001086 A1* 1/2 008 Sriv astav a et al. . . . . . . . . 2 50/3 61 R
WatertOWn, MA ( Us) 2 008/0111083 A1* 5/2 008 Ko ndo et al. . . . . . . . . . . . . 2 50/3 70. 11
2 008/013 13 47 A1* 6/2 008 Sriv astav a et al. . . . . . . . . . . . . 42 3 /2 63
( * ) N o tice: Su bj ect to any disclaimer, the term o f this 2 009/0166585 A1 * 7/2 009 Bto u lnet' co u rchesne 2 52 /3 01 4 H
patent is extended o r adj u sted u nder 3 5 e a' " " " " " " " " " " " '
U. S. C. 154( b) by 164 day s. F OREIGN PATEN T DOCUMEN TS
W0 WO 2 005/068585 A1 7/2 005
( 2 1) App1. N o . : 12 /405, 168
OTHER PUBLICATION S
( 2 2 ) F iled: Mar. 16, 2 009
Bessiere et al. , Lu minescence and Scintillatio n Pro perties o f the
_ _ Small Band Gap Co mpo u nd Lal3 : Ce3 + , N u cl. Instr" . Meth. Phy s. Res.
Related US. Applicatio n Data A 53 712 2 2 6 ( 2 005)
( 63 ) co ntinu atio ndmpart o f applicatio n N O 1 1/93 8 176 Biro wo su to et al. , Scintillatio n Pro perties o f Lu l3 : Ce3 + - High Light
? led o n N OV 9 2 007 HOW Pat N O 7 655 919 and 2 ; Y ield Scintillato rs, IEEE Trans. N u cl. Sci. 52 : 1114- 1118 ( 2 005) .
co ntinu atio n- in- part o f applicatio n N o . 11/93 8, 182 , ( Co ntinu ed)
? led o n N o v . 9, 2 007.
( 60) Pro v isio nal applicatio n N o . 61/045, 891, ? led o n Apr. Primary Examiner i Dav ld P Po m
17 2 008 Assistant Examiner * Dj u ra Malev ic
( 74) Atto rney , Agent, o r F irm * Kilpatrick To wnsend &
( 51) Int, Cl, Sto ckto n LLP
G01 T 1/2 0 ( 2 006. 01)
( 52 ) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 50/3 70. 11; 2 50/3 61 R ( 57) ABSTRACT
( 58) F ield o f Classi? catio n Search . . . . . . . . . . . . . . 2 50/3 7011 The present inv entio n relates to scintillato r co mpo sitio ns and
See applicatio n ? le f o r co mplete search histo ry . related dev ices and metho ds. The scintillato r may inclu de, f o r
example, a mixed scintillato r co mpo sitio n inclu ding at least
( 56) Ref erences Cited tWo dif f erent CsXLa halide co mpo u nds and a do pant,
Wherein X is N a o r Li. Related radiatio n detectio n dev ices and
U- S- PATEN T DOCUMEN TS metho ds are f u rther inclu ded.
5, 3 67, 176 A * 11/1994 Leblans et al. . . . . . . . . . . . . . . . . 2 50/585
6, 585, 913 B2 * 7/2 003 Ly o ns et al. . . . . . . . . . . . . . . . 2 52 /3 01. 5 18 Claims, 5 Drawing Sheets
A 3 . v - 1 B 1. 0 . .
Cs, N aGdEa: 2 % Ce Cs2 N aLaBr? : 0. 2 /6Ce
9_ S15 2 2 s
. 5 , 5 AE ~ 111/n
g I 5. 4
E 1 Q2
: 5G0 mes speeim
no 100 2 00 3 00 100 500 ( m0 100 2 00 3 00
MCA channel MCAd- u annel
C10 . . 1 D 0. 5 . . . .
% CS2 N aLal6S5 /6Ce f , Csz N aLu ls: 1 % Ce
E5 " To r. So eu ra ' g 5 /' cs Spectra '
515 / 12 ~ 5. 2 5% - I
844 ~ 5
' 3 $ 2 11152 3 . 514. '
S3 3 >
% . 2 - % . 1 1
( m 0" ) 0 100 2 00 3 00 400 600 o 2 00 1100 1500 so n 1000
MCAchanneI MCAd' nannei
US 7, 977, 645 B1
Page 2
OTHER PUBLICATION S
Biro Wo su tu et al. , Scintillatio n Pro perties and Ano malo u s
Ce3 + Emissio n o f Cs2 N aREBr6: Ce3 + ( RE: La, Y , Lu ) , J ' . Phy s.
Co ndens. Matter 18: 613 3 - 6148 ( 2 006) .
Bo llinger and Tho mas, Measu rement o f the Time Dependence o f
Scintillatio n Intensity by a Delay ed- Co incidence Metho d, Rev . Sci.
Instr" . 3 2 : 1044- 1050 ( 1961) .
Co mbes et al. , Optical and Scintillatio n Pro perties o f Pu re and
Ce3 + - do ped Csz LiY Cl6 and Li3 Y Cl6: Ce3 + cry stals, J ' . Lu min.
82 : 2 99- 3 05 ( 1999) .
Do renbo s et al. , N o n- Pro po rtio nality in the Scintillatio n Respo nse
and the Energy Reso lu tio n Obtainable With Scintillatio n Cry stals,
IEEE Trans. N u cl. Sci. 42 : 2 190- 2 2 02 ( 1995) .
Gu illo t- N o el et al. , Scintillatio n Pro perties o f RbGdZBr7 : Ce Adv an
tages and Limitatio ns, IEEE Trans. N u cl. Sci. 46: 12 74- 12 84 ( 1999) .
Oo men et al. , On the Lu minescence o f the Sb3 + io n in CsZN aMBr6
( MISc, Y , La) , . 1. Phy s. C. So lid State Phy s. 2 0: 1161- 1 171 ( 1987) .
Ro dny i et al. , Lu minescence Pro perties o f Ce- do ped Csz LiLaCl6
Cry stals, J ' . Lu min. 86: 161- 166 ( 2 000) .
Ro dny i, Pro gress in F ast Scintillato rs, Rad. Measu n 3 3 : 605- 614
( 2 001) .
Van Lo ef et al. , Scintillatio n and Spectro sco py o f the Pu re and
Ce3 + - do ped elpaso lites: CsZLiY X6 ( XICl, Br) , J ' . Phy s. . ' Co ndens.
Matter 14: 8481- 8596 ( 2 002 ) .
* cited by examiner
US. Patent J u l. 12 , 2 011 Sheet 4 o f 5 US 7, 977, 645 B1
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US. Patent J u l. 12 , 2 011 Sheet 5 o f 5 US 7, 977, 645 B1
F IGURE 5
US 7, 977, 645 B1
1
MIXED CESIUM SODIUM AN D LITHIUM
HALIDE SCIN TILLATOR COMPOSITION S
CROSS REF EREN CES TO RELATED
APPLICATION S
The present applicatio n is a co ntinu atio n- in- part o f US.
applicatio n Ser. N o . 11/93 8, 176, entitled Cesiu m and
Lithiu m- Co ntaining Qu aternary Co mpo u nd Scintillato rs,
? led o n N o v . 9, 2 007 no w US. Pat. N o . 7, 655, 919, and a
co ntinu atio n- in- part o f U. S. applicatio n Ser. N o . 1 1/93 8, 182 ,
entitled Cesiu m and So diu m- Co ntaining Scintillato r Co m
po sitio ns, ? led o n N o v . 9, 2 007, and claims prio rity to US.
Pro v isio nal Applicatio n N o . 61/045, 891, ? led Apr. 17, 2 008,
the entire co ntent o f each o f Which is inco rpo rated herein by
ref erence.
The present applicatio n is related to US. Applicatio n N o .
12 , 405, 13 7, entitled Cesiu m and Lithiu m- Co ntaining Qu a
ternary Co mpo u nd Scintillato rs, ? led o n Mar. 16, 2 009 and
US. applicatio n Ser. N o . 12 /405, 155, entitled Cesiu m and
So diu m- Co ntaining Scintillato r Co mpo sitio ns, ? led o n Mar.
16, 2 009, each o f Which is being ? led co ncu rrently hereWith,
the f u ll disclo su res o f Which are inco rpo rated herein by ref
erence.
BACKGROUN D OF THE IN VEN TION
The present inv entio n relates to scintillato r co mpo sitio ns
and related dev ices and metho ds. Mo re speci? cally , the
present inv entio n relates to scintillato r co mpo sitio ns inclu d
ing a scintillatio n co mpo u nd and a do pant f o r u se, f o r
example, in radiatio n detectio n, inclu ding gamma- ray spec
tro sco py , and X- ray and neu tro n detectio n, imaging applica
tio ns, and the like.
Scintillatio n spectro meters are Widely u sed in detectio n
and spectro sco py o f energetic pho to ns ( e. g. , X- ray s, gamma
ray s, etc. ) . Su ch detecto rs are co mmo nly u sed, f o r example,
in nu clear and particle phy sics research, medical imaging,
dif f ractio n, no n destru ctiv e testing, nu clear treaty v eri? catio n
and saf egu ards, nu clear no n- pro lif eratio n mo nito ring, and
geo lo gical explo ratio n.
Impo rtant req u irements f o r the scintillatio n cry stals u sed in
these applicatio ns inclu de high light o u tpu t, transparency to
the light it pro du ces, high sto pping ef ? ciency , f ast respo nse,
go o d pro po rtio nality , lo W co st, and av ailability in large v o l
u me. These req u irements o n the Who le canno t be met by
many o f the co mmercially av ailable scintillato r co mpo si
tio ns. While general classes o f chemical co mpo sitio ns may be
identi? ed as po tentially hav ing so me attractiv e scintillatio n
characteristic( s) , speci? c co mpo sitio ns/f o rmu latio ns hav ing
bo th scintillatio n characteristics and phy sical pro perties nec
essary f o r actu al u se in scintillatio n spectro meters and v ario u s
practical applicatio ns hav e pro v en dif ? cu lt to predict. Spe
ci? c scintillatio n pro perties are no t necessarily predictable
f ro m chemical co mpo sitio n alo ne, and preparing ef f ectiv e
scintillato r co mpo sitio ns f ro m ev en candidate materials o f ten
pro v es dif ? cu lt. F o r example, While the co mpo sitio n o f
so diu m chlo ride had been kno Wn f o r many y ears, the inv en
tio n by Ho f stadter o f a high light- y ield and co nv ersio n e? i
ciency scintillato r f ro m so diu m io dide do ped With thalliu m
lau nched the era o f mo dern radiatio n spectro metry . Mo re than
half a centu ry later, thalliu m do ped so diu m io dide, in f act, still
remains o ne o f the mo st Widely u sed scintillato r materials.
Since the inv entio n o f N aI( Tl) scintillato rs in the 1940 s, f o r
half a centu ry radiatio n detectio n applicatio ns hav e depended
to a signi? cant extent o n this material. The ? elds o f nu clear
medicine, radiatio n mo nito ring, and spectro sco py hav e
2 0
2 5
3 0
3 5
40
45
50
55
60
65
2
gro Wn u p su ppo rted by N aI( Tl) . Altho u gh f ar f ro m ideal,
N aI( Tl) Was relativ ely easy to pro du ce f o r a reaso nable co st
and in large v o lu me. With the adv ent o f X- ray CT in the
1970 s, a maj o r co mmercial ? eld emerged as did a need f o r
dif f erent scintillato r co mpo sitio ns, as N aI( Tl) Was no t able to
meet the req u irements o f CT imaging. Later, the co mmercial
iZatio n o f po sitro n emissio n to mo graphy ( PET) imaging pro
v ided the impetu s f o r the dev elo pment o f y et ano ther class o f
detecto r materials With pro perties su itable f o r PET. As the
metho do lo gy o f scintillato r dev elo pment ev o lv ed, neW mate
rials hav e been added, and y et, speci? c applicatio ns are still
hampered by the lack o f scintillato rs su itable f o r particu lar
applicatio ns.
As a resu lt, there is co ntinu ed interest in the search f o r neW
scintillato r co mpo sitio ns and f o rmu latio ns With bo th the
enhanced perf o rmance and the phy sical characteristics
needed f o r u se in v ario u s applicatio ns. To day , the dev elo p
ment o f neW scintillato r co mpo sitio ns co ntinu es to be as
mu ch an art as a science, since the co mpo sitio n o f a giv en
material do es no t necessarily determine its pro perties as a
scintillato r, Which are stro ngly in? u enced by the histo ry ( e. g. ,
f abricatio n pro cess) o f the material as it is f o rmed. While it
may be po ssible to rej ect a po tential scintillato r f o r a speci? c
applicatio n based so lely o n co mpo sitio n, it is ty pically dif ?
cu lt to predict Whether ev en a material With a pro mising
co mpo sitio n can be u sed to pro du ce a u sef u l scintillato r With
the desired pro perties.
One o f the u ses o f radiatio n mo nito ring dev ices is prev ent
ing the spread o f Weapo ns o f mass destru ctio n su ch as nu clear
Weapo ns. One Way to passiv ely determine the presence o f
nu clear Weapo ns is to detect and identif y the characteristic
signatu res o f special nu clear materials ( SN Ms) su ch as highly
enriched u raniu m and Weapo ns grade plu to niu m. Character
istic X- ray s and gamma- ray s are signatu res o f these materi
als. The general appro ach to a passiv e gamma- ray assay is to
acq u ire raW spectra, co rrect the spectra f o r rate- related elec
tro nic lo sses and so u rce attenu atio n, and co mpu te the to tal
co rrected co u nt rate, Which is pro po rtio nal to the mass o f the
iso to pe being assay ed. The pro po rtio nality co nstant inclu des
the ef f ects o f gamma- ray emissio n rate, so lid angle, and
detecto r ef ? ciency .
Mo nito ring f o r bo th highly enriched u raniu m and Weapo ns
grade plu to niu m inv o lv es analy sis o f X- ray and gamma- ray
spectra With mu ltiple energies o f interest. One impo rtant co n
sideratio n in SN M mo nito ring is the determinatio n o f u ra
niu m enrichment since highly enriched u raniu m can be u sed
f o r dev elo pment o f nu clear Weapo ns. The natu rally o ccu rring
iso to pic abu ndance o f u raniu m is: 2 3 8U ( 99. 2 7% ) , 2 3 5U
( 0. 72 0% ) and 2 3 4U ( 0. 006% ) . When the f ractio n o f the ? ssile
2 3 5 U is higher than that in natu rally o ccu rring u raniu m, the
u raniu m is said to be enriched. The relativ e intensity o f 185. 7
keV gamma- ray s ( f ro m 2 3 5U) co mpared to the 94- 98 keV
X- ray s f o r u raniu m in an u nattenu ated spectru m can be u sed
to determine u raniu m enrichment ( Passiv e N o ndestru ctiv e
Assay o f N u clear Materials, eds. Reilly et al. , US. N u clear
Regu lato ry Co mmissio n, Washingto n DC, pp. 11- 18,
( 1991) ) . As the u raniu m enrichment lev el increases, the rela
tiv e intensity o f the 185. 7 keV gamma- ray peak increases in
co mpariso n to the 94- 98 keV X- ray peak. Ano ther co nsider
atio n in SN M mo nito ring is to distingu ish Weapo ns- grade
plu to niu m ( With 93 % 2 3 9Pu ) f ro m reacto r- grade plu to niu m
<60% 2 3 9Pu ) . The reacto r- grade plu to niu m inclu des o ther
iso to pes su ch as 2 40Pu , 2 41Pu , 2 42 Pu , and 2 3 8Pu . Co mpariso n
o f gamma- ray signatu res o f 2 3 9Pu ( su ch as 12 9. 3 keV and
413 . 7 keV pho to ns) With tho se f o r o ther plu to niu m iso to pes
allo Ws determinatio n o f the grade o f plu to niu m. In additio n to
the characteristic X- and gamma- ray s o f highly enriched u ra
US 7, 977, 645 B1
3
niu m and Weapo ns grade plu to niu m, there is co nsiderable
interest in the measu rement o f irradiated f u el f ro m nu clear
reacto rs becau se o f the plu to niu m pro du ced du ring reacto r
o peratio n. Du e to v ery intense gamma- ray s emitted by ? ssio n
pro du cts o f the irradiated f u el, gamma- ray s f ro m spo ntane
o u s decay o f plu to niu m and u raniu m ( 2 3 5 U, 2 3 9Pu and 2 41Pu )
are generally no t u sed f o r measu rement o f irradiated f u el. The
mo st co mmo nly measu red ? ssio n pro du ct gamma- ray is the
662 keV line f ro m 13 7Cs. Recent threat o f dirty bo mbs
( dev ices Which spread radio activ e material u sing co nv en
tio nal, no n- nu clear explo siv es) has also created an interest in
mo nito ring o f radio activ e materials su ch as 13 7Cs, 60Co ,
2 41Am, radio activ e medical Waste, and irradiated f u el f ro m
nu clear reacto rs that emit high energy gamma- ray s.
Thu s, gamma- ray spectro meters and radiatio n detecto rs
are impo rtant to o ls in mo nito ring o f special nu clear materials.
A nu mber o f ho meland secu rity sy stems su ch as hand- held
radio iso to pe identi? ers, v ehicle po rtals f o r radiatio n detec
tio n, and perso nal radiatio n detectio n dev ices rely o n av ail
ability o f high perf o rmance gamma- ray spectro meters. Simi
lar sy stems are also req u ired f o r nu clear no n- pro lif eratio n
mo nito ring. An impo rtant challenge in ho meland secu rity
mo nito ring is no t o nly to detect hidden radio activ e materials
bu t also to distingu ish them f ro m ro u tinely u sed radio phar
maceu ticals as Well as f ro m natu rally o ccu rring benign radio
activ e materials.
Existing scintillato r materials and co mmercial radiatio n
detecto rs do no t meet the cu rrent needs f o r radiatio n mo ni
to ring and Weapo ns detectio n. F o r example, existing scintil
lato r co mpo sitio ns and detecto rs ty pically lack the o ne o r
mo re impo rtant scintillatio n pro perties ( e. g. , high energy
reso lu tio n, light o u tpu t, sto pping po Wer, f ast respo nse, and
the like) that are desired and/o r are no t u sef u l in detecting
bo th energetic pho to ns ( e. g. , gamma- ray s and X- ray s) as Well
as neu tro n emissio n. Thu s, a need exists f o r impro v ed scin
tillato r co mpo sitio ns su itable f o r u se in v ario u s radiatio n
detectio n applicatio ns, inclu ding, f o r example, radiatio n and
nu clear Weapo ns mo nito ring.
BRIEF SUMMARY OF THE IN VEN TION
The present inv entio n pro v ides scintillato r co mpo sitio ns,
inclu ding mixtu res o f dif f erent q u aternary scintillato r co m
po u nds, and related dev ices and metho ds. In o ne embo di
ment, scintillato r co mpo sitio ns o f the inv entio n can, f o r
example, inclu de o ne o r mo re co mpo u nds selected f ro m
Cs2 N aLaBr6, Cs2 N aGdI6, Cs2 N aLaI6, and Cs2 N aLu I6. These
materials hav e in co mmo n a q u aternary co mpo sitio n co m
prising Cs and N a, a Lanthanide and a Halide. In ano ther
embo diment, a scintillato r co mpo sitio n can inclu de materials
that hav e in co mmo n a q u aternary co mpo u nd co mpo sitio n
co mprising Cs, Li, La and a Halide. Exemplary scintillato r
co mpo sitio ns can, f o r example, inclu de Cs2 LiLaF 6,
Cs2 LiLaCl6, Cs2 LiLaBr6, and Cs2 LiLaI6. Scintillato r co m
po sitio ns o f the present inv entio n can inclu de a single ty pe o f
scintillato r co mpo u nd o r a mixtu re o f dif f erent co mpo u nds
( e. g. , mixed scintillato r co mpo sitio ns) . Mixed scintillato r
co mpo sitio ns can inclu de o ne o r mo re o f the cesiu m and
so diu m- co ntaining q u aternary co mpo u nds disclo sed herein,
o r o ne o r mo re o f the cesiu m and lithiu m- co ntaining q u ater
nary co mpo u nds disclo sed herein. In ano ther embo diment,
e. g. , a co mpo sitio n can inclu de a mixed co mpo sitio n that
inclu des at least tWo dif f erent CsXLa halide co mpo u nds,
Where X is N a o r Li. Exemplary halides can inclu de F , Cl, Br,
o r I.
Excellent scintillatio n pro perties, inclu ding high light o u t
pu t, go o d pro po rtio nality , f ast respo nse, and go o d energy
2 0
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reso lu tio n hav e been measu red f o r certain co mpo sitio ns o f
the present inv entio n, Which Were demo nstrated to be su itable
f o r gamma- ray spectro sco py , as Well as X- ray and neu tro n
emissio n detectio n. Scintillato r co mpo sitio ns as described
herein are cu bic ( and theref o re easy to gro W) ty pically hav e
high light o u tpu t and f ast respo nse. F o r gamma ray s, the
no n- pro po rtio nality is particu larly o u tstanding and can trans
late into go o d energy reso lu tio n. These materials hav e v ery
go o dno n- pro po rtio nality ( e. g. , abo u t 2 % no n- pro po rtio nality
o v er 60 to 1000 keV energy range) . The scintillato r co mpo
sitio ns sho W o u tstanding light o u tpu t f o r neu tro ns in co mpari
so n to prev io u sly existing neu tro n scintillato rs and can sho W
pu lse shape discriminatio n betWeen neu tro ns and gamma
ray s. Thu s, these materials additio nally adv antageo u sly co m
bine excellent gamma- ray detectio n pro perties alo ng With
neu tro n detectio n.
Scintillatio n pro perties o f the certain cry stals/co mpo si
tio ns o f the present inv entio n and described herein inclu de
peak emissio n Wav elengths f ro m abo u t 3 85 to abo u t 475 nm,
Which is Well matched to PMTs as Well as silico n dio des u sed
in nu clear instru mentatio n and a peak Wav elength f o r gamma
ray spectro sco py . The principal decay - time co nstant in o ne
instance Was measu red at appro ximately 50 ns, Which is f aster
than the decay - time co nstant o f co mmercial scintillato rs su ch
as BGO and GSO ( see, e. g. , Table l inf ra) . Thu s, in o ne
embo diment, the present inv entio n inclu des scintillato r co m
po sitio ns hav ing decay time co nstants better than, o r hav ing a
v alu e o f less than, 2 00 ns ( e. g. , less than 150 ns) . In so me
embo diments, the decay time co nstant can be better than 100
ns, o r ev en better than 50 ns. Under gamma ray excitatio n, the
light o u tpu t ty pically Will be greater than abo u t 10, 000 pho
to ns/MeV, and in so me instances greater than abo u t 2 0, 000,
40, 000, o r 60, 000 pho to ns/MeV ( e. g. , ranging f ro m abo u t
17, 000 to abo u t 60, 000 pho to ns/MeV and greater) , Which is
greater than that o f many Widely u sed co mmercial scintilla
to rs.
One aspect o f the present inv entio n inclu des a scintillato r
co mpo sitio n inclu ding a scintillatio n co mpo u nd and a
do pant. Scintillatio n co mpo u nds can inclu de a co mpo u nd
With the f o rmu la xl - x2 - x3 - x4. In certain embo diments, xl can
inclu de Cs, x2 can inclu de N a, x3 can inclu de La, Gd, o r Lu ,
and x4 can inclu de a halide. In so me embo diments, the scin
tillato r co mpo sitio n can inclu de a single do pant o r a mixtu re
o f do pants. Scintillato r co mpo sitio ns o f the present inv entio n
can inclu de a mixtu re o f dif f erent co mpo u nds ( e. g. , q u ater
nary co mpo u nds) disclo sed herein, su ch as mixed scintillato r
co mpo sitio ns inclu ding tWo o r mo re dif f erent CsXLa halide
co mpo u nds, Where X is N a o r Li.
In ano ther aspect, the inv entio n f u rther inclu des dev ices,
su ch as a radiatio n detectio n dev ice hav ing a scintillato r co m
po sitio n inclu ding a scintillatio n co mpo u nd and a do pant; and
a pho to detecto r assembly o ptically co u pled to the scintillato r
co mpo sitio n. The pho to detecto r assembly can inclu de, f o r
example, a pho to mu ltiplier tu be, a pho to dio de, o r a PIN
detecto r. The dev ice may f u rther inclu de a data analy sis, o r
co mpu ter, sy stem f o r pro cessing and analy Zing detected sig
nals.
In y et ano ther aspect, the inv entio n inclu des an X- ray and
neu tro n detecto r assembly , inclu ding a scintillato r co mpo si
tio n inclu ding a scintillatio n co mpo u nd and a do pant, a pho
to detecto r assembly , and electro nics o r a sy stem f o r data
pro cessing/analy sis. F o r example, the dev ice can inclu de
electro nics co n? gu red f o r perf o rming pu lse- shape analy sis to
dif f erentiate gamma ray f ro m neu tro n emissio ns.
In y et ano ther aspect, the inv entio n inclu des a metho d o f
perf o rming radiatio n detectio n. Su ch a metho d can inclu de,
f o r example, pro v iding a detectio n dev ice hav ing a detecto r
US 7, 977, 645 B1
5
assembly inclu ding a scintillato r co mpo sitio n inclu ding a
scintillatio n co mpo u nd and a do pant; a pho to detecto r assem
bly ; and po sitio ning a target Within a ? eld o f v ieW o f the
scintillato r as to detect emissio ns f ro m the target. Emissio ns
can inclu de, f o r example, gamma- ray , X- ray , o r neu tro n emis
sio ns. A target can inclu de v ario u s po tential so u rces o f detect
able emissio ns inclu ding neu tro n emitters ( e. g. , plu to niu m
and the like) , gamma- ray so u rces ( e. g. , u raniu m and the like) ,
X- ray so u rces, etc. In o ne embo diment, f o r example, the
scintillato r co mpo sitio ns can be u sed f o r imaging applica
tio ns inclu ding medical imaging su ch as in a metho d o f per
f o rming PET ( e. g. , time- o f - ? ight PET) o r SPECT. In su ch an
embo diment, the imaging metho d can co mprise inj ecting o r
o therWise administering a patient With a detectable label, and,
af ter a su f ? cient perio d o f time to allo W lo caliZatio n o r dis
tribu tio n o f the label, placing the patient Within the ? eld o f
v ieW o f the detectio n dev ice. Thu s, in so me embo diments the
target inclu des a patient o r a po rtio n o f a patient s bo dy .
F o r a f u ller u nderstanding o f the natu re and adv antages o f
the present inv entio n, ref erence sho u ld be had to the ensu ing
detailed descriptio n taken in co nj u nctio n With the acco mpa
ny ing draWings. The draWings represent embo diments o f the
present inv entio n by Way o f illu stratio n. The inv entio n is
capable o f mo di? catio n in v ario u s respects Witho u t departing
f ro m the inv entio n. Acco rdingly , the draWings/? gu res and
descriptio n o f these embo diments are illu strativ e in natu re,
and no t restrictiv e.
BRIEF DESCRIPTION OF THE DRAWIN GS
F IG. 1A thro u gh 1D depict 13 7Cs spectra co llected With
Cs2 N aGdI6: 2 % Ce ( F IG. 1A) , Cs2 N aLaBr6: O. 2 % Ce ( F IG.
1B) , Cs2 N aLaI6: 5% Ce ( F IG. 1C) , and Cs2 N aLu I6: 1% Ce
( F IG. 1D) scintillato r co mpo sitio ns co u pled to a PMT. The
energy reso lu tio ns o f a 662 keV peak f o r Cs2 N aGdI6: 2 % Ce,
Cs2 N aLaBr6: 0. 2 % Ce, Cs2 N aLaI6: 5% Ce, and Cs2 N aLu I6:
1% Ce are 7. 6% , 11% , 5. 2 5% , and 8. 5% ( F WHM) , respec
tiv ely . F IGS. 1A, 1C, and 1D f u rther depict 13 7Cs spectra f o r
BGO co u pled to a PMT.
F IG. 2 A thro u gh 2 D depict o ptical emissio n spectra f o r
Cs2 N aGdI6: Ce ( F IG. 2 A) , Cs2 N aLaBr6: Ce ( F IG. 2 B) ,
Cs2 N aLaI6: Ce ( F IG. 2 C) , and Cs2 N aLu I6: Ce ( F IG. 2 D) scin
tillato r co mpo sitio ns u po n expo su re to X- ray s. F IGS. 2 A and
2 D sho W o ptical emissio n spectra f o r 1% and 2 % Ce With
Cs2 N aGdI6: Ce and Cs2 N aLu I6: Ce, respectiv ely .
F IG. 3 A thro u gh 3 C depict time pro ? les f o r Cs2 N aGdI6:
2 % Ce ( F IG. 3 A) , Cs2 N aLaI6: 5% Ce ( F IG. 2 B) , and
Cs2 N aLu I6: 1% Ce ( F IG. 2 C) expo sed to gamma ray s. Rise
times ( 1, ) f o r Cs2 N aGdI6: 2 % Ce, Cs2 N aLaI6: 5% Ce, and
Cs2 N aLu I6: 1% Ce Were 0. 85 ns, 4 ns, and 0. 85 ns, respec
tiv ely , in certain embo diments. Principal decay times ( u d1) f o r
Cs2 N aGdI6: 2 % Ce, Cs2 N aLaI6: 5% Ce, and Cs2 N aLu I6: 1%
Ce Were 55 ns, 50 ns, and 3 5 ns, respectiv ely .
F IG. 4A thro u gh 4C illu strate no n- pro po rtio nality f o r
Cs2 N aGdI6: 2 % Ce ( F IG. 4A) , Cs2 N aLaI6: 5% Ce ( F IG. 4B) ,
and Cs2 N aLu I6: 1% Ce ( F IG. 4C) scintillato r co mpo sitio ns.
The ? gu re sho Ws light o u tpu t o f the scintillato r co mpo sitio ns
measu red u nder excitatio n f ro m iso to pes su ch as 2 41Am ( 60
keV y - ray s) , 57Co ( 12 2 keV y - ray s) , 2 2 N a ( 511 keV and 12 75
keV y - ray s) , and 13 7Cs ( 662 keV y - ray s) .
F IG. 5 is a schematic diagram o f a detecto r assembly o f the
present inv entio n.
DETAILED DESCRIPTION OF THE IN VEN TION
This inv entio n Will be better u ndersto o d With reso rt to the
f o llo Wing de? nitio ns:
2 0
2 5
3 0
3 5
40
45
50
55
60
65
6
A. Rise time, in ref erence to a scintillatio n cry stal material,
shall mean the speed With Which its light o u tpu t gro Ws o nce a
gamma- ray has been sto pped in the cry stal. The co ntribu tio n
o f this characteristic o f a scintillato r co mbined With the decay
time co ntribu te to a timing reso lu tio n.
B. A F ast timing scintillato r ( o r f ast scintillato r) ty pically
inclu des a timing reso lu tio n o f abo u t 500 ps o r less. F o r
certain PET applicatio ns ( e. g. , time- o f - ? ight ( TOF ) ) , the f ast
scintillato r sho u ld be capable o f lo caliZing an annihilatio n
ev ent as o riginating f ro m Within abo u t a 3 0 cm distance, i. e. ,
f ro m Within a hu man being scanned.
C. Timing accu racy o r reso lu tio n, u su ally de? ned by the
f u ll Width half maximu m ( F WHM) o f the time o f arriv al
dif f erences f ro m a po int so u rce o f annihilatio n gamma- ray s.
Becau se o f a nu mber o f f acto rs, there is a spread o f measu red
v alu es o f times o f arriv al, ev en When they are all eq u al.
Usu ally they distribu te alo ng a bell- shaped o r Gau ssian
cu rv e. The F WHM is the Width o f the cu rv e at a height that is
half o f the v alu e o f the cu rv e at its peak.
D. Light Ou tpu t shall mean the nu mber o f light pho to ns
pro du ced per u nit energy depo sited by the detected gamma
ray , ty pically the nu mber o f light pho to ns/MeV.
E. Sto pping po Wer o r attenu atio n shall mean the range o f
the inco ming X- ray o r gamma- ray in the scintillatio n cry stal
material. The attenu atio n length, in this case, is the length o f
cry stal material needed to redu ce the inco ming beam ? u x to
1/e' .
F . Pro po rtio nality o f respo nse ( o r linearity ) . F o r so me
applicatio ns ( su ch as CT scanning) it is desirable that the light
o u tpu t be su bstantially pro po rtio nal to the depo sited energy .
F o r applicatio ns su ch as spectro sco py , no n- pro po rtio nality o f
respo nse is an impo rtant parameter. In a ty pical scintillato r,
the nu mber o f light pho to ns pro du ced per MeV o f inco ming
gamma- ray energy is no t co nstant. Rather, it v aries With the
energy o f the sto pped gamma- ray . This has tWo deleterio u s
ef f ects. The ? rst is that the energy scale is no t linear, bu t it is
po ssible to calibrate f o r the ef f ect. The seco nd is that it
degrades energy reso lu tio n. To see ho W this o ccu rs, co nsider
a scintillato r that pro du ces 3 00 pho to ns at 150 keV, 160
pho to ns at 100 keV and 60 pho to ns at 50 keV. F ro m statistics
alo ne, the energy reso lu tio n at 150 keV sho u ld be the v ari
ability in 3 00 pho to ns, Which is 5. 8% , o r 8. 7 keV. If ev ery
detected ev ent depo sited 150 keV in o ne step this Wo u ld be
the case. On the o ther hand, if , as it o ccu rs, an ev ent depo sited
100 keV in a ? rst interactio n and then ano ther 50 keV in a
seco nd interactio n, the nu mber o f pho to ns pro du ced Wo u ld
no t be 3 00 o n the av erage, bu t 160+ 60: 2 2 0 pho to ns, f o r a
dif f erence o f 80 pho to ns o r 2 7% . In mu ltiple detectio ns, the
peak Wo u ld bro aden Well bey o nd the theo retical 8. 7 keV. The
smaller the no n- pro po rtio nality the smaller this bro adening
and the clo ser the actu al energy reso lu tio n appro aches the
theo retical limit.
The scintillatio n co mpo sitio ns o f the present inv entio n Will
respo nd by emitting light af ter detecting charged particles,
high energy pho to ns, and f o r so me embo diments, neu tro ns,
thereby pro v iding u sef u l scintillatio n pro perties. The scintil
latio n co mpo u nd has the f o rmu la, xl- x2 - x3 - x4, and can
inclu de Cs as x1, N a as x2 , La, Gd, o r Lu as x3 , and a halide
su ch as Br o r I as x4. Gd has a large neu tro n cro ss- sectio n. In
certain embo diments, a do pant as speci? ed in the speci? ca
tio n and claims, can be added to the scintillato r co mpo sitio n.
In certain embo diments, the scintillatio n co mpo u nd elements
exist in ato mic ratio s o f 2 : 1: 1: 6 With a do pant, su ch as
Cs2 N aGdI6: 2 % Ce.
Scintillato r co mpo sitio ns can inclu de a single q u aternary
co mpo u nd selected f ro m tho se described herein o r a mixtu re
o f dif f erent co mpo u nds described herein. Co mpo sitio ns can,
US 7, 977, 645 B1
7
e. g. , inclu de mixed scintillato r co mpo sitio ns With at least tWo
dif f erent CsXLa halide co mpo u nds, Where X is N a o r Li.
Thu s, mixed scintillato r co mpo sitio ns can inclu de a mixtu re
o f at least tWo q u aternary co mpo u nds hav ing N a o r Li at the
seco nd po sitio n, su ch that the q u aternary co mpo u nd mixtu re
inclu des, f o r example, Cs( N a, Li) La halide. Halides can
inclu de, f o r example, F , Cl, Br, o r I. Certain embo diments can
f u rther inclu de mixed scintillato r co mpo sitio ns that inclu de a
mixtu re o f at least tWo q u aternary co mpo u nds hav ing N a o r Li
at the seco nd po sitio n and at least tWo dif f erent halides at the
f o u rth po sitio n, su ch that the q u aternary co mpo u nd mixtu re
inclu des, f o r example, Cs( N a, Li) La( Cl, Br) o r any o ther po s
sible co mbinatio n o f halides and N a and Li. Thu s, as dif f erent
co mpo u nds may hav e dif f erent scintillatio n characteristics,
o ne adv antage o f the present inv entio n inclu des the ability to
select o r cu sto miZe a particu lar mixed co mpo sitio n ratio o r
f o rmu latio n, Where a particu lar selectio n o r f o rmu latio n is at
least partially based o n intended u se o f the scintillato r co m
po sitio n and/ o r desired pro perties o r scintillatio n/perf o r
mance characteristics. F o r example, a particu lar mixed q u a
ternary co mpo u nd co mpo sitio n ( e. g. , mixed CsXLa halide
co mpo sitio n su ch that X is N a o r Li) f o rmu latio n may be
selected based o n o ne o r mo re o f a v ariety o f f acto rs, su ch as
desired sto pping po Wer ( e. g. , at least partially as a f u nctio n o f
ato mic nu mber) , neu tro n respo nse, bandgap lev els tu ning/
o ptimiZatio n f o r Ce emissio n and light o u tpu t, pu lse shape
discriminatio n, gamma- ray sensitiv ity , and the like.
The scintillato r co mpo sitio ns o f the inv entio n are particu
larly u sef u l, f o r example, f o r spectro sco py detectio n o f ener
getic pho to ns ( e. g. , X- ray s, gamma- ray s) , as Well as f o r neu
tro n emissio n detectio n. N o table characteristics f o r the
scintillatio n co mpo sitio ns o f the inv entio n inclu de su rpris
ingly ro bu st light o u tpu t, high gamma- ray and neu tro n sto p
ping ef ? ciency ( attenu atio n) , f ast respo nse, and go o d no n
pro po rtio nality . F u rthermo re, the scintillato r co mpo sitio ns
can be e? iciently and eco no mically pro du ced. Thu s, detec
to rs hav ing scintillato r co mpo sitio ns described in the present
inv entio n are u sef u l in a Wide v ariety o f applicatio ns, inclu d
ing Witho u t limitatio n nu clear and high energy phy sics
research, medical imaging, dif f ractio n, no n- destru ctiv e test
ing, nu clear treaty v eri? catio n and saf egu ards, and geo lo gical
explo ratio n.
The scintillato r co mpo sitio n o f the present inv entio n can
o ptio nally inclu de a do pant . Do pants can af f ect certain
pro perties, su ch as phy sical pro perties ( e. g. , brittleness, etc. )
as Well as scintillatio n pro perties ( e. g. , lu minescence, etc. ) o f
the scintillato r co mpo sitio n. The do pant can inclu de, f o r
example, ceriu m ( Ce) , praseo dy miu m ( Pr) , lu tetiu m ( Lu ) ,
lanthanu m ( La) , eu ro piu m ( Eu ) , samariu m ( Sm) , stro ntiu m
( Sr) , thalliu m ( Tl) , chlo rine ( Cl) , ? u o rine ( F ) , io dine ( I) , and
mixtu res o f any o f the do pants. The amo u nt o f do pant present
Will depend o n v ario u s f acto rs, su ch as the applicatio n f o r
Which the scintillato r co mpo sitio n is being u sed; the desired
scintillatio n pro perties ( e. g. , emissio n pro perties, timing
reso lu tio n, etc. ) ; and the ty pe o f detectio n dev ice into Which
the scintillato r is being inco rpo rated. F o r example, the do pant
is ty pically emplo y ed at a lev el in the range o f abo u t 0. 1% to
abo u t 2 0% , by mo lar Weight. In certain embo diments, the
amo u nt o f do pant is in the range o f abo u t 0. 1 % to abo u t 100% ,
o r abo u t 0. 1% to abo u t 5. 0% , o r abo u t 5. 0% to abo u t 2 0% , by
mo lar Weight.
The scintillato r co mpo sitio ns o f the inv entio n may be pre
pared in sev eral dif f erent f o rms. In so me embo diments, the
co mpo sitio n is in a cry stalline f o rm ( e. g. , mo no cry stalline) .
Scintillatio n cry stals, su ch as mo no cry stalline scintillato rs,
hav e a greater tendency f o r transparency than o ther f o rms.
Scintillato rs in cry stalline f o rm ( e. g. , scintillatio n cry stals)
2 0
2 5
3 0
3 5
40
45
50
55
60
65
8
are o f ten u sef u l f o r high- energy radiatio n detecto rs, e. g. ,
tho se u sed f o r gamma- ray o r X- ray detectio n. Ho Wev er, the
co mpo sitio n can inclu de o ther f o rms as Well, and the selected
f o rm may depend, in part, o n the intended end u se o f the
scintillato r. F o r example, a scintillato r can be in a po Wder
f o rm. It can also be prepared in the f o rm o f a ceramic o r
po ly cry stalline ceramic. Other f o rms o f scintillatio n co mpo
sitio ns Will be reco gniZed and can inclu de, f o r example,
glasses, depo sits, v apo r depo sited ? lms, micro co lu mnar, o r
o ther f o rms su itable f o r radiatio n detectio n as described
herein. It sho u ld also be u ndersto o d that a scintillato r co m
po sitio n might co ntain small amo u nts o f impu rities. Also ,
mino r amo u nts o f o ther materials may be pu rpo sef u lly
inclu ded in the scintillato r co mpo sitio ns to af f ect the pro per
ties o f the scintillato r co mpo sitio ns.
Metho ds f o r making cry stal materials can inclu de tho se
metho ds described herein and may f u rther inclu de o ther tech
niq u es. Ty pically , the appro priate reactants are melted at a
temperatu re su ? icient to f o rm a co ngru ent, mo lten co mpo si
tio n. The melting temperatu re Will depend o n the identity o f
the reactants themselv es ( see, e. g. , melting po ints o f reac
tants) , bu t is u su ally in the range o f abo u t 3 000 C. to abo u t
13 500 C. N o n- limiting examples o f the cry stal- gro Wing
metho ds can inclu de certain techniq u es o f the Bridgman
Sto ckbarger metho ds; the CZo chralski metho ds, the Zo ne
melting metho ds ( o r ? o ating Zo ne metho d) , the v ertical
gradient f reeZe ( V GF ) metho ds, and the temperatu re gradient
metho ds. See, e. g. , Example 1 inf ra. ( see also , e. g. , Lu mi
nescent Materials , by G. Blasse et al, Springer- Verlag ( 1994)
and Cry stal Gro Wth Pro cesses , by J . C. Brice, Blackie &
So n Ltd ( 1986) ) .
In the practice o f the present inv entio n, attentio n is paid to
the phy sical pro perties o f the scintillato r material. In particu
lar applicatio ns, pro perties su ch as hy gro sco py ( tendency to
abso rb Water) , brittleness ( tendency to crack) , and cru mbli
ness sho u ld be minimal.
TABLE I
Pro perties o f Scintillato rs
Wav e
Light length Principal
Ou tpu t Of Rise- Decay
( Pho to ns/ Density Emissio n time Time
Material MeV) ( gcm3 ) ( nrn) ( ns) ( ns)
N aI( Tl) 3 8, 000 3 . 67 415 > 10 2 3 0
CsI( Tl) 52 , 000 4. 51 540 > 10 1000
LSO 2 4, 000 7. 4 42 0 <1 40
BGO 8, 2 00 7. 13 505 > 1 3 00
BaF 2 10, 000 4. 88 3 10, slo W <0. 1 62 0, slo W
~ 2 , 000 2 2 0, f ast 0. 6, f ast
f ast
GSO 7, 600 6. 7 43 0 ~ 8 60
CdWO4 15, 000 8. 0 480 5000
Y AP 2 0, 000 5. 55 3 70 <1 2 6
Cs2 N aLaBr6: Ce 12 , 000 3 . 91 3 86 3 0 55
Cs2 N aGdI6 Ce 2 6, 000 ~ 4 43 1 0. 85 55
Cs2 N aLaI6: Ce 49, 000 ~ 4 42 9 4 50
Cs2 N aLu I6: Ce 2 7, 000 4. 6 42 8 0. 85 3 5
Table I pro v ides a listing o f certain pro perties o f a nu mber
o f scintillato rs. Co mpared to o ther co mmercially av ailable
scintillato rs, inclu ding CsI, Which is amo ng the scintillatio n
materials With the highest kno Wn light o u tpu t, the scintillato r
co mpo sitio ns o f these inv entio ns pro du ce co mparable light
o u tpu t. In additio n, they hav e a f ast principal decay - time
co nstant.
As set f o rth abo v e, scintillato r co mpo sitio ns o f the present
inv entio n may ? nd u se in a Wide v ariety o f applicatio ns. In
US 7, 977, 645 B1
o ne embo diment, f o r example, the inv entio n is directed to a
metho d f o r detecting energy radiatio n ( e. g. , gamma- ray s,
X- ray s, neu tro n emissio ns, and the like) With a scintillatio n
detecto r inclu ding the scintillatio n co mpo sitio n o f the inv en
tio n.
F IG. 5 is a schematic diagram o f a detecto r assembly o f the
present inv entio n. The detecto r 10 inclu des a scintillato r 12
o ptically co u pled to a light pho to detecto r 14 o r imaging
dev ice. The detecto r assembly 10 can inclu de a data analy sis,
o r co mpu ter, sy stem 16 to pro cess inf o rmatio n f ro m the scin
tillato r 12 and light pho to detecto r 14. In u se, the detecto r 10
detects energetic radiatio n emitted f o rm a so u rce 18.
A data analy sis, o r co mpu ter, sy stem thereo f can inclu de,
f o r example, a mo du le o r sy stem to pro cess inf o rmatio n ( e. g. ,
radiatio n detectio n inf o rmatio n) f ro m the detecto r/pho to de
tecto rs can also be inclu ded in an inv entio n assembly and can
inclu de, f o r example, a Wide v ariety o f pro prietary o r co m
mercially av ailable co mpu ters, electro nics, o r sy stems hav ing
o ne o r mo re pro cessing stru ctu res, a perso nal co mpu ter,
mainf rame, o r the like, With su ch sy stems o f ten co mprising
data pro cessing hardWare and/ o r so f tWare co n? gu red to
implement any o ne ( o r co mbinatio n o f ) the metho d steps
described herein. Any so f tWare Will ty pically co mprise
machine readable co de o f pro gramming instru ctio ns embo d
ied in a tangible media su ch as a memo ry , a digital o r o ptical
reco rding media, o ptical, electrical, o r Wireless telemetry sig
nals, o r the like, and o ne o r mo re o f these stru ctu res may also
be u sed to transmit data and inf o rmatio n betWeen co mpo
nents o f the sy stem in any o f a Wide v ariety o f distribu ted o r
centraliZed signal pro cessing architectu res.
The detecto r assembly ty pically inclu des material f o rmed
f ro m the scintillato r co mpo sitio n described herein ( e. g. , o ne
o r mo re scintillato r cry stals) . The detecto r f u rther can
inclu de, f o r example, a light detectio n assembly inclu ding
o ne o r mo re pho to detecto rs. N o n- limiting examples o f pho
to detecto rs inclu de pho to mu ltiplier tu bes ( PMT) , pho to
dio des, CCD senso rs, image intensi? ers, and the like. Cho ice
o f a particu lar pho to detecto r Will depend in part o n the ty pe o f
radiatio n detecto r being f abricated and o n its intended u se o f
the dev ice. In certain embo diments, the pho to detecto r may be
po sitio n- sensitiv e.
The detecto r assemblies themselv es, Which can inclu de the
scintillato r and the pho to detecto r assembly , can be co nnected
to a v ariety o f to o ls and dev ices, as mentio ned prev io u sly .
N o n- limiting examples inclu de nu clear Weapo ns mo nito ring
and detectio n dev ices, Well- lo gging to o ls, and imaging
dev ices, su ch as nu clear medicine dev ices ( e. g. , PET) . Vari
o u s techno lo gies f o r o perably co u pling o r integrating a radia
tio n detecto r assembly co ntaining a scintillato r to a detectio n
dev ice can be u tiliZed in the present inv entio n, inclu ding
v ario u s kno Wn techniq u es.
The detecto rs may also be co nnected to a v isu aliZatio n
interf ace, imaging eq u ipment, o r digital imaging eq u ipment
( e. g. , pixilated ? at panel dev ices) . In so me embo diments, the
scintillato r may serv e as a co mpo nent o f a screen scintillato r.
F o r example, po Wdered scintillato r material co u ld be f o rmed
into a relativ ely ? at plate, Which is attached to a ? lm, su ch as
pho to graphic ? lm. Energetic radiatio n, e. g. , X- ray s, gamma
ray s, neu tro n, o riginating f ro m a so u rce, Wo u ld interact With
the scintillato r and be co nv erted into light pho to ns, Which are
v isu aliZed in the dev elo ped ? lm. The ? lm can be replaced by
amo rpho u s silico n po sitio n- sensitiv e pho to detecto rs o r o ther
po sitio n- sensitiv e detecto rs, su ch as av alanche dio des and the
like.
Imaging dev ices, inclu ding medical imaging eq u ipment,
su ch as the PET and SPECT dev ices, and the like, represent
ano ther impo rtant applicatio n f o r inv entio n scintillato r co m
2 0
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3 5
40
45
50
55
60
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10
po sitio ns and radiatio n detecto rs. F u rthermo re, geo lo gical
explo ratio n dev ices, su ch as Well- lo gging dev ices, Were men
tio ned prev io u sly and represent an impo rtant applicatio n f o r
these radiatio n detecto rs. The assembly co ntaining the scin
tillato r u su ally inclu des, f o r example, an o ptical Windo W at
o ne end o f the enclo su re- casing. The Windo W permits radia
tio n- indu ced scintillatio n light to pass o u t o f the scintillato r
assembly f o r measu rement by the pho to n detectio n assembly
o r light- sensing dev ice ( e. g. , pho to mu ltiplier tu be, etc. ) ,
Which is co u pled to the scintillato r assembly . The light- sens
ing dev ice co nv erts the light pho to ns emitted f ro m the scin
tillato r into electrical pu lses that may be shaped and digitiZed,
f o r example, by the asso ciated electro nics. By this general
pro cess, gamma- ray s can be detected, Which in tu rn pro v ides
an analy sis o f geo lo gical f o rmatio ns, su ch as ro ck strata su r
ro u nding the drilling bo re ho les.
In many o f the applicatio ns o f a scintillato r co mpo sitio n as
set f o rth abo v e ( e. g. , nu clear Weapo ns mo nito ring and detec
tio n, imaging, and Well- lo gging and PET techno lo gies) , cer
tain characteristics o f the scintillato r are desirable, inclu ding
high light o u tpu t, f ast rise time and sho rt decay time, go o d
timing reso lu tio n, and su itable phy sical pro perties. The
present inv entio n is expected to pro v ide scintillato r materials
that can pro v ide the desired high light o u tpu t and initial
pho to n intensity characteristics f o r demanding applicatio ns
o f the techno lo gies. Mo reo v er, the inv entio n scintillato r co m
po sitio ns are also expected to simu ltaneo u sly exhibit the
o ther impo rtant pro perties no ted abo v e, e. g. , sho rt decay time
and go o d sto pping po Wer. F u rthermo re, the scintillato r mate
rials are also expected to be pro du ced e? iciently and eco
no mically , and also expected to be emplo y ed in a v ariety o f
o ther dev ices Which req u ire radiatio n/ signal detectio n ( e. g. ,
gamma- ray , X- ray , neu tro n emissio ns, and the like) .
The f o llo Wing examples are intended to illu strate bu t no t
limit the inv entio n.
EXAMPLES
Example 1
The present example pro v ides a metho d f o r gro Wing and
pro v ides characteriZatio n f o r the scintillato r co mpo sitio n
cry stals. The f o llo Wing examples are o f f ered by Way o f illu s
tratio n, no t by Way o f limitatio n.
Cry stal Gro Wth o f Co mpo u nds Exempli? ed With
Cs2 N aLaBr6, Cs2 N aGdI6, Cs2 N aLaI6, and CsZN aLu I6
In o ne example, a o ne Zo ne Bridgman f u rnace Was u sed f o r
cry stal gro Wth. Ty pical gro Wth rates f o r the Bridgman pro cess
are abo u t l- 6 mm/ho u r. Gro Wth rates ranging f ro m abo u t 1
mm/day to abo u t 1 cm/ho u r may be u tiliZed. The range o f
rates may be extended to impro v e material q u ality .
Cs2 N aLaBr6, Cs2 N aGdI6, Cs2 N aLaI6, and Cs2 N aLu I6
hav e a cu bic cry stal stru ctu re. The densities o f Cs2 N aLaBr6,
Cs2 N aGdI6, Cs2 N aLaI6, and Cs2 N aLu I6 are betWeen abo u t
3 . 9 and abo u t 4. 6 g/cm3 . The co mpo sitio ns melt co ngru ently
at appro ximately 78, 92 5, 778, and 10500 C. , respectiv ely ,
and theref o re their cry stals can be gro Wn u sing melt based
metho ds su ch as tho se described by Bridgman and CZo chral
ski. These melt- based pro cesses are Well su ited f o r gro Wth o f
large v o lu me cry stals ( Brice, Cry stal Gro wth Pro cesses,
Blackie Halsted Press ( 1986) ) . The Bridgman metho d has
been u sed f o r gro Wing Cs2 N aLaBr6, Cs2 N aGdI6, Cs2 N aLaI6,
and Cs2 N aLu I6. Bo th the v ertical and ho riZo ntal o rientatio ns
o f the Bridgman metho d can be u sed in pro du cing cry stals o f
the present inv entio n. In certain embo diments, the v ertical
Bridgman metho d Was u sed in pro du cing cry stals examined
and discu ssed belo W.
US 7, 977, 645 B1
11
Cs2 N aLaBr6: Single cry stals o f this material Were gro wn
by the Bridgman techniq u e in v ertical silica ampo u les u nder
v acu u m. Starting materials Were CsBr ( Aldrich, anhy dro u s,
99. 9% ) , N aBr ( Aldrich, anhy dro u s, 99. 9% ) , and LaBr3 ( Ald
rich, anhy dro u s, 99. 99+ % ) .
Cs2 N aGdl6: Single cry stals o f this material Were gro Wn by
the Bridgman techniq u e in v ertical silica ampo u les u nder
v acu u m. Starting materials Were Csl ( Aldrich, anhy dro u s,
99. 9% ) , N al ( Aldrich, anhy dro u s, 99. 9% ) , and Gdl3 ( Aldrich,
anhy dro u s, 99. 99+ % ) .
Cs2 N aLal6: Single cry stals o f this material Were gro Wn by
the Bridgman techniq u e in v ertical silica ampo u les u nder
v acu u m. Starting materials Were Csl ( Aldrich, anhy dro u s,
99. 9% ) , N al ( Aldrich, anhy dro u s, 99. 9% ) , and Lal3 ( Aldrich,
anhy dro u s, 99. 99+ % ) .
Cs2 N aLu l6: Single cry stals o f this material Were gro Wn by
the Bridgman techniq u e in v ertical silica ampo u les u nder
v acu u m. Starting materials Were Csl ( Aldrich, anhy dro u s,
99. 9% ) , N al ( Aldrich, anhy dro u s, 99. 9% ) , and Lu l3 ( Aldrich,
anhy dro u s, 99. 99+ % ) .
Scintillatio n Pro perties o f Scintillato r Co mpo sitio ns
Scintillatio n pro perties o f small Bridgman gro Wn scintil
latio n co mpo sitio n cry stals ( 2 3 00 m3 ) hav e been charac
teriZed. This inv estigatio n inv o lv ed measu rement o f the light
o u tpu t, the emissio n spectru m, and the scintillatio n decay
time o f the cry stals. Energy reso lu tio n o f sample cry stals and
their pro po rtio nality o f respo nse Were also measu red.
1. Light Ou tpu t and Energy Reso lu tio n
As sho Wn in F IGS. 1A, B, C, and D, the energy reso lu tio n
o f the 662 keV pho to peak reco rded With the scintillato r co m
po sitio ns has been measu red to be in the v icinity o f 7. 6% ,
11% , 5. 2 5% , and 8. 5% ( F WHM) at ro o m temperatu re f o r
Cs2 N aGdl6: 2 % Ce, Cs2 N aLaBr6: 0. 2 % Ce, Cs2 N aLal6: 5%
Ce, and Cs2 N aLu l6: 1% Ce, respectiv ely . The light o u tpu t o f
scintillato r co mpo sitio n cry stals Was measu red by co mparing
their respo nse to 662 keV y - ray s ( 13 7Cs so u rce) to the
respo nse o f a BGO scintillato r to the same iso to pe ( see F IGS.
1A, C, and D) . This measu rement inv o lv ed o ptical co u pling
o f a scintillato r cry stal to a pho to mu ltiplier tu be ( With mu lti
alkali S- 2 0 pho to catho de) , irradiating the scintillato r With
662 keV pho to ns, and reco rding the resu lting pu lse height
spectru m. In o rder to maximiz e light co llectio n, the scintilla
to r co mpo sitio n cry stal Was Wrapped in re? ectiv e White
Te? o n tape o n all f aces ( except the o ne co u pled to the PMT) .
An index matching silico ne ? u id Was also u sed at the PMT
scintillato r interf ace. A pu lse height spectru m Was reco rded
With a scintillato r co mpo sitio n cry stal. This experiment Was
then repeated With a BGO scintillato r. Co mpariso n o f the
pho to peak po sitio n o btained With the scintillato r co mpo sitio n
f o r 662 keV pho to n energy to that With BGO pro v ided esti
matio n o f light o u tpu t f o r the scintillato r co mpo sitio n cry stal.
F IGS. 1 A, B, C, and D sho W the pu lse height spectra f o r a
scintillato r co mpo sitio n u nder 13 7Cs irradiatio n and ampli? er
shaping time o f 4. 0 u s. This shaping time is lo ng eno u gh to
allo W f u ll light co llectio n f ro m bo th the scintillato rs. The
PMT bias and ampli? er gain Were the same f o r bo th spectra.
Based o n the reco rded pho to peak po sitio ns f o r each scintil
lato r co mpo sitio n and BGO, light o u tpu t o f Cs2 N aGdl6: 2 %
Ce, Cs2 N aLaBr6: 0. 2 % Ce, Cs2 N aLal6: 5% Ce, and
Cs2 N aLu l6: 1% Ce cry stals Was estimated to be abo u t 2 6, 500
pho to ns/MeV, 12 , 000 pho to ns/MeV, 48, 500 pho to ns/MeV,
and 2 7, 000 pho to ns/MeV, respectiv ely .
2 . Emissio n Spectru m
N o rmaliz ed emissio n spectra f o r the scintillato r co mpo si
tio ns are sho Wn in F IGS. 2 A thro u gh 2 D. The scintillato r
co mpo sitio n samples Were excited With radiatio n f ro m a Phil
ips X- ray tu be hav ing a Cu target, With po Wer settings o f 40
2 0
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50
55
60
65
12
kVp and 2 0 mA. The scintillatio n light Was passed thro u gh a
McPherso n mo no chro mato r and detected by a pho to mu lti
plier tu be. The peak emissio n Wav elength f o r the Cs2 N aGdl6:
Ce, Cs2 N aLaBr6: Ce, Cs2 N aLal6z Ce, and Cs2 N aLu l6z Ce
samples Was at appro ximately 43 1 nm, 3 86 nm, 42 9 nm, and
42 8 nm, respectiv ely . Peak emissio n Wav elengths in this
range are attractiv e f o r gamma- ray spectro sco py becau se they
match Well With the spectral respo nse o f the pho to mu ltiplier
tu bes as Well as a neW generatio n o f silico n pho to dio des.
3 . Time Pro ? les
F IGS. 3 A, B, and C sho W the time pro ? les reco rded f o r
Cs2 N aGdl6: 2 % Ce, Cs2 N aLal6: 5% Ce, and Cs2 N aLu l6: 1%
Ce samples, respectiv ely . Time pro ? les o f the scintillato r
co mpo sitio ns hav e been measu red u nder gamma ray excita
tio n u sing the delay ed co incidence metho d ( Bo llinger and
Tho mas, Rev . Sci. Instr. 3 2 : 1044 ( 1961) ) . F o r Cs2 N aGdl6: 2 %
Ce, the rise time o f the scintillatio n pu lse is ~ 0. 85 ns and the
principal decay time is abo u t 55 ns. F o r Cs2 N aLal6: 5% Ce,
the rise time o f the scintillatio n pu lse is ~ 4 ns and the principal
decay time is abo u t 50 ns. F o r Cs2 N aLu l6: 1% Ce, the rise
time o f the scintillatio n pu lse is ~ 0. 85 ns and the principal
decay time is abo u t 3 5 ns. F IGS. 3 A- C also sho W seco ndary ,
slo Wer decay co mpo nents present in time pro ? les.
4. N o n- Pro po rtio nality
As sho Wn in F IGS. 4 A, B, and C, the no n- pro po rtio nality
o f Cs2 N aGdl6: 2 % Ce, Cs2 N aLal6: 5% Ce, and Cs2 N aLu l6:
1% Ce scintillato r co mpo sitio ns Was ev alu ated, respectiv ely .
N o n- pro po rtio nality ( as a f u nctio n o f energy ) in light y ield
can be o ne o f the impo rtant reaso ns f o r degradatio n in energy
reso lu tio n o f established scintillato rs su ch as N al( Tl) and
Csl( Tl) ( Do renbo s et al. , IEEE Trans. N u c. Sci. 42 : 2 190
( 1995) ) . Light o u tpu t o f the scintillato r co mpo sitio ns Was
measu red u nder excitatio n f ro m iso to pes su ch as 2 41Am ( 60
keV y - ray s) , 57Co ( 12 2 keV, 13 6 keV, and 14. 4 keV y - ray s) ,
2 2 N a ( 511 keV and 12 75 keV y - ray s) and 13 7Cs ( 662 keV
y - ray s) . The test cry stals Were Wrapped in Te? o n tape and
co u pled to a PMT. Pu lse height measu rements Were per
f o rmed u sing standard N IM eq u ipment With the scintillato r
expo sed to dif f erent radio iso to pes. The same settings Were
u sed f o r the PMT and pu lse pro cessing electro nics f o r each
iso to pe. F ro m the measu red peak po sitio n and the kno Wn
y - ray energy f o r each iso to pe, the light o u tpu t ( in pho to ns/
MeV) at each y - ray energy Was estimated. The data po ints
Were then no rmaliZed With respect to the light o u tpu t v alu e at
662 keV energy and the resu lts ( sho Wn in F IGS. 4 A, B, and
C) indicated that Cs2 N aGdl6: 2 % Ce, Cs2 N aLal6: 5% Ce, and
Cs2 N aLu l6: 1% Ce Were v ery pro po rtio nal scintillato rs. Ov er
in the energy range f ro m abo u t 60 to abo u t 12 75 keV, the
no n- pro po rtio nality in light y ield Was less than abo u t 5% ,
ty pically betWeen abo u t 2 to 3 % ( f o r co rrespo nding v alu es f o r
o ther established scintillato rs see, e. g. , Gu illo t- N o el et al. ,
IEEE Trans. N u c. Sci 46: 12 74- 12 84 ( 1999) ) .
Ov erall, these measu rements indicated that the scintillato r
co mpo sitio ns as described in the present inv entio n hav e high
light o u tpu t, f ast respo nse and sho W go o d q u alities in terms o f
light o u tpu t, energy reso lu tio n, speed and exceptio nal no n
pro po rtio nality .
Altho u gh the inv entio n has been described With ref erence
to the abo v e examples, it Will be u ndersto o d that mo di? ca
tio ns and v ariatio ns are enco mpassed Within the spirit and
sco pe o f the inv entio n. Acco rdingly , the inv entio n is limited
o nly by the f o llo Wing claims alo ng With their f u ll sco pe o f
eq u iv alents. All pu blicatio ns and patent do cu ments cited in
this applicatio n are inco rpo rated by ref erence in their entirety
f o r all pu rpo ses to the same extent as if each indiv idu al
pu blicatio n o r patent do cu ment Were so indiv idu ally deno ted.
US 7, 977, 645 B1
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What is claimed is:
1. A mixed scintillato r co mpo sitio n, co mprising at least
tWo dif f erent CsXLa halide co mpo u nds and a do pant,
Wherein X is N a o r Li.
2 . The scintillato r o f claim 1, Wherein the dif f erent CsXLa
halide co mpo u nds are selected f ro m Cs2 N aLaF 6,
Cs2 N aLaCl6, Cs2 N aLaBr6, Cs2 N aLal6, Cs2 LiLaF 6,
Cs2 LiLaCl6, Cs2 LiLaBr6, and Cs2 LiLal6.
3 . The scintillato r o f claim 1, Wherein the do pant co mprises
Ce.
4. The scintillato r o f claim 1, Wherein the do pant is present
at less than abo u t 2 0% by mo lar Weight.
5. The scintillato r co mpo sitio n o f claim 1, Wherein the
do pant co mprises Ce present at eq u al to o r less than abo u t 5%
by mo lar Weight.
6. The scintillato r o f claim 1, Wherein the scintillato r co m
prises a cry stalline, ceramic, o r po ly cry stalline ceramic f o rm.
7. A radiatio n detectio n dev ice, co mprising a mixed scin
tillato r co mpo sitio n co mprising at least tWo dif f erent CsXLa
halide co mpo u nds and a do pant, Wherein X is N a o r Li; and a
pho to detecto r assembly o ptically co u pled to the scintillato r.
8. The dev ice o f claim 7, Wherein the pho to detecto r assem
bly co mprises a pho to mu ltiplier tu be, a pho to dio de, a PIN
detecto r, charge- co u pled dev ice, o r an av alanche detecto r.
9. The dev ice o f claim 7, f u rther co mprising a radiatio n
so u rce.
10. The dev ice o f claim 7, f u rther co mprising a co mpu ter
sy stem co u pled to the pho to detecto r assembly so that the
co mpu ter o u tpu ts image data in respo nse to detected radia
tio n.
2 0
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14
11. The dev ice o f claim 10, Wherein the co mpu ter co m
prises instru ctio ns f o r co nstru cting an image f ro m detected
radiatio n.
12 . The dev ice o f claim 7, Wherein the dev ice is co n? gu red
to detect x- ray s, gamma- ray s, o r a co mbinatio n thereo f .
13 . The dev ice o f claim 7, Wherein the dev ice co mprises a
scintillato r co mpo sitio n co mprising Li and the dev ice is co n
? gu red to detect x- ray s, gamma- ray s, neu tro ns, o r any co m
binatio n thereo f .
14. A metho d o f perf o rming radiatio n detectio n, co mpris
ing:
pro v iding a detectio n dev ice co mprising a mixed scintilla
to r co mpo sitio n co mprising at least tWo dif f erent CsXLa
halide co mpo u nds and a do pant, Wherein X is N a o r Li;
and a pho to detecto r assembly o ptically co u pled to the
scintillato r; and
po sitio ning the dev ice su ch that a radiatio n so u rce is Within
a ? eld o f v ieW o f the scintillato r co mpo sitio n so as to
detect emissio ns f ro m the so u rce.
15. The metho d o f claim 14, Wherein the emissio ns co m
prise gamma- ray o r X- ray emissio ns.
16. The metho d o f claim 14, Wherein the scintillato r co m
po sitio n co mprises Li and the emissio ns co mprise neu tro n
emissio ns.
17. The metho d o f claim 14, Wherein a patient is po sitio ned
betWeen the radiatio n so u rce and the scintillato r co mpo sitio n.
18. The metho d o f claim 14, Wherein the radiatio n so u rce
co mprises a patient.