Synthesis and Screening of the System SrO-Gd O -Al O Dopedwith Tb by Polymerized-Complex Combinatorial Chemistry O -Al O SrO-Gd Tb

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2001, Vol. 45, No. 5

Printed in the Republic of Korea

461

Tb

SrO-Gd

2

O

3

-Al

2

O

3

* ^† ^‡

, ^† , ^‡

(2001. 7. 26 )

Synthesis and Screening of the System SrO-Gd

2

O

3

-Al

2

O

3

Doped with Tb by Polymerized-Complex Combinatorial Chemistry

Yang Sun Jeong*, Chang Hae Kim, Hee Dong Park, Joon Taik Park^†, and Sung Kwon Kang^‡ Advanced Material Division, Korea Research Institute of Chemistry Technology, Taejon 305-600, Korea

†Department of Chemistry, Korea Advanced Institute of Science and Technology, Taejon 306-701, Korea

‡Department of Chemistry, Chung Nam University, Taejon 305-764, Korea

Received July 26, 2001)

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^ _`Y a6 ,b UV PL(Photoluminescence) VUV(Vacuum-UV: 147nm) PL^ cd"

e :! ;f"<(. g !6 ,b@ hd! i-8j XRDk SEM '1" lm"+ no"

<(. UV PL cd h, 240 nm "*# Sr0.6Gd0.12Al0.17Tb0.1Oδ, 275 nm "*# Sr0.03-

Gd0.89Al0.03Tb0.06Oδk Sr^0.6Gd0.12Al0.17Tb0.1OδeY+ 307 nm "*# Sr^0.03Gd0.89Al0.03Tb0.06Oδ@ !*

543 nm@ p9 ?q rF stu(. eY+ VUV PL cd h# Gd^1-x-yAlxTbyOδ: 0.595<x<0.733, 0.016<y<0.017 eY+ SrxAl1-x-yTbyOδ: 0.049<x<0.064, 0.02<y<0.039@ !vw* 543 nm@ p9 ? q rF stu(. ' !@ x& 89/# plasma display panel y1 qz"(.

ABSTRACT. The combinatorial approach has been applied to discover and optimize the composition of the novel or enhanced materials. In this study, we screened the optimum composition of the system SrO-Gd2O3- Al2O3 doped with Tb³⁺ by a polymerized-complex combinatorial chemistry method. Mixtures with compositions of Sr, Gd and Al component that is in the range from 0 to 1 in about 0.05 increments could be tested. The sample powders were synthesized by a polymerized complex method. To prepare appropriately polymeric precursors, we used the metallic nitrates, citric acid and ethylene glycol. The luminescence properties of the synthesized powders are investigated using the UV and VUV (Vacuum-UV: 147 nm) photoluminescence spectrometer. In addition, the crystallinity and morphology of powder were monitored by X-ray diffraction spectrometer and scanning electron microscopy. In result of VUV PL works, there are good luminescent samples with the composition of 0.595<x<0.733 and 0.016<y<0.017 in Gd1-x-yAlxTbyOδ and 0.049<x<0.064 and 0.02<y<0.039 in SrxAl1-x-yTbyOδ, their materials can be applicable to plasma display panels as the green phosphor.

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0@ => d å4'(. JK'L 1S

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(99.9%) çèk T x [1"<+, citric acid(CA, 99.5%)k ethylene glycol(EG, 99.8%)@ é

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!P QR 6 ml³' >n ©©@ !ê

ÝF JK'L1S, CAk EG é1S ,ô , Table 1. Flow diagram of the polymerized-complex combi-

natorial chemistry method

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|, | ) ,á, hdj(XRD) U i-8j

(SEM) ,á' qz ¼ ×¤ ØÙR !L4 k

! ,w ö¶ =>¼ q ~Ï(.

ëìí qîï eY+ ð£ñ T@ Ü!

,7* 23 q @ 230 § UV PL cd h, | QR p9 ë'

JC ¸R¶# p¼ ~Ï(. 1100^oC^ T

,w* \`Y"+, 5% H²/N2 (300cc/min) , w* 1200^oC^ 3 _`Y ³ ±* :

!' (¢ @ " Fig. 1 stÏ(.

e* stu' H/@ ! Q¢ :!

QR |' («F st (. jy]^ ½

p9 ?E $# , |' 240 nm*#

@ !' Sr⁰Gd0.73Al0.2Tb0.07Oδ (#29)Ò '+, 275 nm*# Sr^0.45Gd0.2Al0.25Tb0.1Oδ (#165) eY+ 307 nm*# Sr0Gd0.92Al0.02Tb0.06Oδ (#2)@ !'Ï(. ë@ H/@ O²⁻ 'L Tb³⁺ 'L ['

@ \- '¨ @ charge transfer band(CTB)k Tb³⁺ 'L@ 4f⁸-4f⁷5d¹ \' !"#q éG $

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ë x& * ⁵D4-⁷Fj \'q sts

#Ë, p9 \' ± 543 nm w( \'q q|

½ p9?E '+ ~(. ' ⁵D4-⁷F5\'^*

Fig. 1. Excitation and emission spectra of SrxGd1-x-y-zAlyTbzOδ.

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Tb³⁺ 'L@ x& p9 ^ ' \' m(.¹⁰

|' H/ QR (« , p9 |

543 nm^ +d)+ | 240, 275 eY+

307 nm* UV PL cd" 230@ §

R'ßYE O!"<(. q| p9 ?q * !

+ T,w* 1200^oC^ \ _`Y , 5% H2/N2 (300cc/min) ,w* 1300^oC^ 3

_`Y 'Ï(. Fig. 2# |' 240 nmÒ

@ R'ßY^º, ;&' ,N p9 ?q

* @£(. ' |]^ - ëì í' }' ³q+ qîï ð£ñ' yF ³

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ø |' 307 nmÒ # qîï' }' ³

q+ ëìí ð£ñ' yF ³ ,*

p9 ?q rF st Fig. 3* / ~] , e ± Sr^0.03Gd0.89Al0.03Tb0.06Oδ@ !* p9 ?q q| rF stu(. g |' 275 nmÒ #

ò ,]^ s01#Ë, |' 240 nmk 307 nm* p9 ?q rF st ,' 2~

Fig. 4* / ~(. q| * ?E $# !

Sr0.03Gd0.89Al0.03Tb0.06Oδk Sr^0.6Gd0.12Al0.17Tb0.1Oδ]^ s tu(.

Fig. 3. Library for the Tb(III) ion under 307 nm excitation in the ternary SrO-Gd2O3-Al2O3 system. Samples were prepared at 1300^oC for 3 h in 5% H2/N2 atmosphere.

Fig. 2. Library for the Tb(III) ion under 240 nm excitation in the ternary SrO-Gd2O3-Al2O3 system. Samples were prepared at 1300^oC for 3 h in 5% H2/N2 atmosphere.

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2001, Vol. 45, No. 5

Fig. 5 Ü!,7@ 230 VUV PL

cd h@ R'ßY'(. !+ +,- ./

\/E 1200^oC^ T ,w* \`Y , 5%

H2/N2 (300cc/min) ,w* 1300^oC^ 3 _`Y

'(. ;&' ¯¼N VUV PL@ |m 147 nm* p9 ?q * @£(. ' ©

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_`Y , VUV PL cd h ± p9

?q * @ !³ h^º 1300^oC

* q| * / ~(.

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* p9 ?q rF sts, ' B êE ? y]^ )# => °"<(.

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¾1 Gd²O3-Al2O3'!,7 23 45

? !,@ B êE (. _`Y ,w E ê" w§* T ,wk 5% H²/N2

(300cc/min) ,w* !"<(. Fig. 8 T , w* ! ³@ VUV PL cd h'(. e

* x÷ ð£ñ@ B ê^ 23@ B ê QR 0~1B 3 òÏ+, qîï, ð£ñ eY+ 23@

Fig. 7. Relative emission intensities under 147 nm excitation as a function of the firing temperature.

Fig. 8. Fine-tuning screening of Gd1-x-yAlxTbyOδ. Samples were prepared in air atmosphere.

Fig. 6. Relative emission intensities of the library under 147 nm excitation in Fig. 5.

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' 1B'¿^ ð£ñ@ B êq çq¼N qî ï@ B ê# 4(. e* sts' 23@

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Gd3Al5O12' A 30%d4 p9 ?q * no¼

~(. Gd4Al2O9 ! 1100^oC* p9 ?q q

| r+ !L4q 6R7N e ?# 8#s, Gd3Al5O12!*# !L4q 6R7N ?q çq§* 1400^oC* À p9 ?E stÏ(.

Fig. 9# 5% H²/N2 (300cc/min) ,w* _`Y

@ VUV PL cd h^º T ,w* _`

Y 9q¶^ Gd0.847Al0.142Tb0.011Oδ(a-Gd4Al2O9) k Gd^0.322Al0.661Tb0.017Oδ(c-Gd3Al5O12) !* p9 ? q :]s, !L4q 1200^oCÒ # Gd⁴Al2O9(a, e) !' Gd3Al5O12(c, d) !( 20% 'j :]s 1300^oC2# ø^ Gd³Al5O12!* e ?q

;< çq"# / ~(. 456 23@ B'

0.01~0.02 ['Ò ?q r¿^ ' , l"

 w@ = -?"F st ' Fig. 10'(.

Fig. 11 Gd^1-x-yAlxTbyOδ? ± 1500^oC(5%

H2/N2 300cc/min)* _`Y @ E >§

¾ XRD@ àÐHÚ'(. Gd^0.847Al0.142Tb0.011Oδ(a)E

6 j Gd⁴Al2O9's Gd²O3@ j' ØÛ } Fig. 9. Fine-tuning screening of Gd1-x-yAlxTbyOδ. Samples

were prepared in 5% H2/N2 (300cc/min) atmosphere.

Fig. 10. Relative emission intensities under 147 nm excitation as a function of the firing temperature.

Fig. 11. XRD patterns of some samples in the fine-tuning screening of Gd1-x-yAlxTbyOδ.

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Fig. 12. SEM photographs of some samples in Fig. 11.

' Ø~# éj'(. Gd0.322Al0.661Tb0.017Oδ(c)k Gd0.311Al0.656Tb0.033Oδ(d)*# Gd3Al5O12' 6 j'+

GdAlO³j' A Ø~(. '# Gd³Al5O12

j' 1500^oC* GdAlO3k Al2O3^ ,§G m

c ê§ GdAlO³j' ù Ø~#Ë, '

!m Gd^0.656Al0.331Tb0.013Oδ(b)*# @ GdAlO³j ]^ st ]^ Ø Gd³Al5O12!* J¤

@s4 j' A3"F G '' 89:!

B= £(# ]^ Î6(.

Fig. 11 a6 i- 8j Fig. 12

stÏ#Ë, ck dE ak b ê§ i-q ÊC G¶ D+ rq ;< ÑÒ (A 2µm) / ~ (. ak b@ # XRD cd h(Fig. 11-a, b)*

4 / ~' éj]^ Ô "+ Ej' }' Ø~# ' i- 8j*4 sts , 'F ªm³

p9 ?4 = # ]^ [6(.

23' 456 R'ßY@ VUV PL cdh^ 2 ¾ p9 ?q * g (¢ !(Sr^0.04Gd0-

Al0.085Tb0.11Oδ)*@ Sr/Al molêk ! L4@

Fig. 13. Fine-tuning screening of SrxAl1-x-yTbyOδ. Samples were prepared in 5% H2/N2 (300cc/min) atmosphere.

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=> ="<(. e h# Fig. 13 ¡(. 23@

Bk @ jn5' Hò 1300^oC* `Y

q p9 ?q rs, 23@ Bq GN À

p9?q Sr/Alêq O H]^ JC '¨"#

no¼ ~Ï(. À+ p9 ?E $#

1300^oC* _`Y ± Sr^0.054Al0.926Tb0.02Oδ(b) !

@ * stu(.

Fig. 14# Sr^xAl1-x-yTbyOδ? ± @

E >§ ¾ XRD àÐHÚ]^* SrAl¹²O19j' E '+, Al2O3 j' éG ~(.

Sr0.034Al0.946Tb0.02Oδ!(a)*# SrAl¹²O19k Al²O3j ' éG~+, Sr^0.089Al0.892Tb0.02Oδ !(c)*#

Al2O3 j' 5¶+ SrAl12O19 j¤ 8!6 no¼

~Ï(. 1400^oC* `Y Sr^0.054Al0.926Tb0.02Oδ

!(b)@ àÐ HÚ Al²O3j' J 2 ~ ]s p9 ?# * = £(¶ D(. ø

¡ ! T ,w* 1500^oC _`Y (b')

!L4q b( 100^oC .4 ú"+ Al²O3

j' ù }' Ø~(. ! `Y"# ' j 8! p9 ? ù 4I' G# ð ~(.

Fig. 15. SEM photographs of some samples in Fig. 14.

Fig. 14. XRD patterns of some samples in the fine-tuning screening of SrxAl1-x-yTbyO_δ.

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e = n 1 ?ym E ·" JK"

%+ 4"+ ~(.

Fig. 14 a6 !@ i- 8j Fig.

15 stÏ(. \8ym SrAl12O19j@ 8m Îj8 ' ¾1+, ?q q| : Sr^0.054Gd0Al0.926Tb0.02Oδ(b)

!' (¢ !³(a, c)( ;< HÚ' ÑÒ

/ ~(. a@ (¢ ê§ i-q ù úÑ ÒË, ' XRD@ ,á h(e 14-a)* /

~' Al²O3j' }' Ô " i-@ !|

= £(# ¡(. !L4q .Ø¶(b') i- r q G¶¶¤ p9 ?# 4"# no¼

~Ï(.

23' 456 SrO-Gd2O3-Al2O37 89

+,- ./ \/E Ã"# 0]^

!"+ %&"<(. => h +,- ./

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# Sr0.6Gd0.12Al0.17Tb0.1Oδ(β-Sr4Al2O7), 275 nmÒ #

Sr0.03Gd0.89Al0.03Tb0.06Oδ(cubic Gd2O3)k Sr^0.6Gd0.12Al0.17Tb0.1Oδ

(β-Sr⁴Al2O7) eY+ 307 nmÒ # Sr^0.03Gd0.89Al0.03Tb0.06Oδ

(cubic Gd2O3)m ]^ stu(.

ø VUV PL@ # Sr⁰Gd0.73Al0.2Tb0.07Oδ, Sr0.04Gd0Al0.85Tb0.11Oδò ^ dYq GÏ(. '

?ym => h, ,w*# Gd1-x-yAlxTbyOδ

# 0.595<x<0.733 eY+ 0.016<y<0.017 *, eY + Sr^xAl1-x-yTbyO# 0.049<x<0.064 eY+ 0.02<y<0.039

* p9?q rF stu(. '³ ±*4

Gd0.322Al0.661Tb0.017Oδ# 1500^oC(5% H2/N2 300cc/min)

* ! ' Gd³Al5O12 j]^* eY+ Sr^0.054 Al0.926Tb0.02Oδ# 1300^oC(5% H2/N2 300 cc/min)* !

' SrAl12O19j]^* q| * p9 ?E $#

x& 89 ¾ ~Ï(. QR* '³ !

6(.

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