Synthesis of Y O :Eu Added the Group 1 or 2 Elements Using Complex-Polymerization and its Luminescent Properties O :Eu 1, 2 Y

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(1)Journal of the Korean Chemical Society 2001, Vol. 45, No. 3 Printed in the Republic of Korea. 1, 2

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(3) . Y2O3 : Eu. . *

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(5) (2001. 2. 7 ). †. †. Synthesis of Y2O3 : Eu Added the Group 1 or 2 Elements Using Complex-Polymerization and its Luminescent Properties Sang Mi Park*, Chang Hae Kim†, Joung Kyu Park†, Hee Dong Park †, and Ho G. Jang Chemistry, Korea University, Seoul 136-701, Korea † Advanced Materials Division, Korea Research Institute of Chemical Technology, Taejon 305-600, Korea (Received February 7, 2001). . Y O : Eu , ! "# $% &' ( ) *+ ,'- .. /01 23 "# $% & 45 678 9&: 2; : <=) .. > ?! @ABC D'EF 100-300 nm 678 Y O : Eu : GHE I, 1J K5 2J

(6) : L2EF MN? OP QREI.. 2. 3. 1-3. 2. 3. ABSTRACT. Europium activated yttrium oxide (Y2O3 : Eu) is extensively applied to red phosphor for Flat Panel Display because of its high efficiency and the thermal and chemical stability. Flat Panel Display screen which have a high resolution and high efficiency needs to the phosphors of ideally small size spherical particle. In this study, we prepared a Y2O3 : Eu phosphor using polymeric precursor methods and investigated the codoping effect by introducing the group 1 or 2 elements to Y2O3 : Eu phosphor in view of improvement of luminance efficiency.. . , S ! "# $% &' ( ) *+ , '- .. Y O 8 T H U yttriumDVD WX8 Y3Z? [\ 6] oxygenDV? 80 ^ _`F cubic C typeD.. a]8 b Y3ZD Uc? [\EX S dD, X Uc? [\ EX C dD e.. fG Y 8 a 23 d g h? 0 i8 j5 k) \le.. Eu (4f ) T m& ?! O ) ^_`F , O ?! n&: opqF nE-nD rs nD(charge-transfer state transition)? 80 t ?u3: v.. wnAx(i): Y2O3 : Eu. 2. 3. 4,5. 6. 3+. 2. 6,7. 2−. 3+. 2−. 6. S H?! wn cy z{(parity selection ? 80 Eu 8 4f |} ~?! n7 & nD (electric dipole transition) 3-3, dD 5 C H?! D F nD8 &7 & nD (magnetic dipole transition)(∆J=1) D F nD8 n7 & nD(electric dipole transition)(∆J=2)2 .. ! dD 5 C H?! n7 & nD D F nD(612 nm)?! 2 M 62 .. /01 23 "# $% & 45 678 9&: 2; : <=) .. w), rwC) GH- 9& 6 6. 3+. rule). 5. 2. 7. 0. 1. 5. 7. 0. 2. 8. 2. 5. 0. 7. 2. 9. 1-3. 236.

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(8) . 72 µm) j5 <=) E, D ) 0 $X m&8 TD M ND e.. , V?! %8 + %) 0 9&8 ¡E, 9&rD ¢£ 0;.. D? w0 ¤ 678 9&(9& w3¥D < 100 nm) , n7, H) ¦5 §. ¨© .. g_ 9&8 672 < 200 nm8 ª ~, T 672 «2? M ¬72 «2.. , M ¬7 T 67 ®¯e.. @ABC D' GHC5 °E, 5 V±?!± BD 21E, 9& 672 4², ³DVD n ~? ´µ /¶·)¸ £ 9 &: ¹ .. g_, 9& 672 º» 4p M ¬7 ) 0 "X M &)8 D'? G o .. D_ Z ]cE7 [0 > ?! F_ 23 1J K5 2J

(9) q L2 Y O : Eu : @ABC D'EF GHE, 8 9& MN? ¼ OP ½\3 ¨p¾& EI.. 10-13. 14. 2. 3. @ABC? 8 ¿À5 Fig. 1? ~Á.. ÂM 'Ã5 > Ä± (Å)?! GH Y O , 2. 3. Y2O3 : Eu. . 237. Eu2O3 , Li2CO3, Na2CO3, K2CO3, MgO, CaCO3, SrC. UU }Æ? ÇF GHEI, Æ (citric acid anhydrous) ?ÈÉ ÊDË(ethylene glycol)? 1:4(mol)k) ÇF ,'EI.. U 'Ã H k? ÌÍ %À®? /Î Ï, !!Ð 135 CÑ3 2EI.. ÒBe ÓÔ 'Ã 80-135 C?! 2 Eµ -X, ÕD «M- Æ ?ÈÉ ÊDË ,D? Ö+?×Ø´ w Ù0 Z± ÓÔ Ú( /& n 2 e.. D n : 1100 C?! /0 %Û /Ü BEI.. @ABC? 80 GH- /Ü8 N H,E7 [0! .Ý j5 /Þ ßEI.. n 8 /0 i H,E7 [EF TG-DTA (Dupont SDT-2960) Analyzer: ,'EF à7 /[7?! 10 C/min8 áVâ±) rV?! 1200 CÑ3 2E X! ®ãEI.. + /Ü8 Tr äE7 [0! X-c åæ/Þ7(Rigaku,8 DMAX-33 X-ray diffraction) ,'EI, /Ü8 9& 67 ç r äE7 [0! Å,n&è½é(scanning electron microscopy, JEOL JSM-840A) ,'EI.. N 5 / ±¯(photoluminescence spectroscopy), 147 nm F7

(10) 2; ;à &êc / ±¯ O3, BaCO3. o. o. o. o. o. (vacuum ultraviolet photoluminescence spectroscopy). ,'EI, ÝcM(cathodoluminescence)5 2 ânëD 800 VD, nì2 1.5 mA E?! íEI... 'Ã? î)¸ Çp ÒBe â ³DVq 5 +ï Æ @BÕ .. D @BÕD ¶e ð8 Æ ?ÈÉ ÊDË 8 ÒB'Ã 80-135 C8 V±ñ[?! !!Ð 2 EX ÕD «ME 7¶2 MEF ÒBe 'Ã D £Eµ òDµ -, V±ó Ö+?× Ø´ wD X!, %? e Õ/&2 G i- °° /& @Õ n 2 q ;.. Dôµ Be /& @Õ n /& TB ~? ³DVqD £Eµ /Æ-µ EF õnD 3 ö±÷ E, ø7ÕD Qµ ù rs?!± F_ ³D VD /& ~? TB·)¸ /+- 3 ö.2 ¯â 2? 80 ³DVq5 T Eµ e .. D jD ³DV8 DD ! + o. 15-20. Fig. 1. Flow chart for a polymeric precursor routes. 2001, Vol. 45, No. 3.

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(13) D <= p, ð8 Æ ,'. é» âDV âDV8 i+2 r) © ! T ? 5 V±: = Eµ - ) ,e.. ! n wV±: [0 âDV? Æ8 û k: 3þ) EF ¿ÀEI.. O : Eu , M (x=0.06 mol)? 1J K5 2J

(14) Y 8 L2ð 0.005ý0.7(mole)) %Û2² B : &êc ;à &êc O8 F7

(15) ? ü MN8 : H,EI.. Table 1? &êc O 8 F7

(16) (254 nm)?!8 M±: ~Á.. +, D L2e é»? û2 «2? M¬72 «2EI, , , g g+ ×D L2e é»? û2 «2? M¬72 EI.. ;à &êc O?!8 M ±: Table 2? ~Á.. $8 T? ´ X 1J

(17) +8 é» 0.05x0.5, 8 é» 0.2x0.4, g+ 8 é» 0.2x0.3 8 ñ[) L2EI ÿ M ±2 «2EI.. 2J

(18) g8 é» 0.05x0.1, 8 é» 0.05x0.3, ×8 é» 0.05x0.1, g + 8 é» 0.05x0.38 ñ[) L2EI ÿ M ±2 «2EI.. g A +D 0.2 mol L2-Á ÿ8 CLT: r ' kEF ¾.. M± r' ¾. ª 110%±8 5 M ¬7: ~Á.. CIE ( $: ®ã T, r' 8 (Ä± x=0.6502, y=0.3455D² +D L2-Á ÿ (Ä± (2-x-y). Fig. 2. TG/DTA curve for the preparation of Y2O3.. ? £ 678 45 9&qD e.. ú â DV? Æ( Æ : ?ÈÉ ÊD Ë=1:4)8 û k? ü ¿À 1ý6(mol)þ8 k) L2EF ¿À T, 1(mol)þ ÿ? ( õnÕD -Á 3(mol)þ Dr?! ÓÔ Ú( n 2 ®ã- ) ¾p, 3þó Ö+? ×Ø´ wD ;ß· ¨ Á.. n 8 /Þ T Fig. 2? ~Á.. µ 8 c (TG) ¾X, 200 CÑ3 !!Ð µ 2 D5 ð8 Õ8 «M /& w? e Õ8 «M? 8 ) Ííe.. 250ý350 C V±?!8 m µ /& @Õ n ~ 8 ø7ÕD /0-X! .. % /Þ(DTA) c ¾X, ¬ ]8 M 62 ®ã- 250 C DE?!8 M6 /& @Õ n ? E }Æ8 /0? 8 ) ¾D², 250ý350 C?! n ~8 ø7Õ8 /0 ÿ ) U- ;.. D 5 µ c?!± äD -Á.. 450ý500 C ?! Y O 8 T? 80 ) #°o. o. o. o. o. 2. 3. 3. x. y. Table 1. Relative emission intensities of Y(2-x-y)O3 : Eux, My (x=0.06 mol) as a function of the concentration of metal at 254 nm Li Na K Mg Ca Sr Ba excitation.. Added ion. Added mol 0 0.05 0.1 0.2 0.3 0.4 0.5. Li. Na. K. Mg. Ca. Sr. Ba. 100 107.94 94.65 100.37 107.75 122.40 128.89. 100 74.23 73.30 84.98 85.61 86.03 90.28. 100 79.04 80.10 97.97 103.95 114.56 121.02. 100 111.20 100.67 68.01 79.74 81.84 76.51. 100 110.54 76.53 101.36 91.53 89.24 90.51. 100 96.59 85.64 82.80 71.12 66.57 57.04. 100 107.10 106.98 101.52 95.38 104.50 105.09. Journal of the Korean Chemical Society.

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(20) . Y2O3 : Eu. . 239. Table 2. Relative emission intensities of Y(2-x-y)O3 : Eux, My (x=0.06 mol) as a function of the concentration of metal under vuv Li Na K Mg Ca Sr Ba (147 nm) excitation.. . Added ion Added mol 0 0.05 0.1 0.2 0.3 0.4 0.5. Li. Na. K. Mg. Ca. Sr. Ba. 100 115.29 136.42 140.75 140.87 143.52 139.96. 100 97.86 105.65 111.07 114.87 112.26 101.09. 100 101.43 106.58 112.40 116.77 103.77 98.00. 100 102.77 105.70 99.85 98.37 96.83 90.31. 100 106.06 118.56 113.34 110.40 102.03 100.55. 100 100.62 106.41 98.66 90.49 81.76 76.74. 100 108.75 110.64 113.42 110.89 97.95 87.30. Fig. 4. X-ray diffraction patterns of Y(2-x-y)O3 : Eux, My (x= 0.06 mol, y=0.2 mol) at 1100 oC none Li Na K Mg Ca Sr Ba.. . . . û2 «2EF± M %&? : Å3 ö.. D5 X-c åæ %& /Þ T?!± !(D, Y O : Eu 8 H )3 ö. ¨ .. F7 ×"# ¾X, 260 nmD E?! *5 + Eu 8 nE nD? 80 ? u3: vEF M E ) , 8 F7 × "# N ~Á.. Fig. 4? 1J K5 2J8

(21) 2 UU 0.2 mol L2E F 1100 C?! 3% +EF ¹5 /Üq8 X-c åæ $³ ~Á.. UU8 åæ $³5 $ a Y O 8 9- H(Ia3 H): ~ .. D 5 L2e DVqD H? OP Å3 ö, M N Pr%. ¨ .. × L2 é» SrY O 8 .ü rD - M± 2 -Á.. w/8 67 9& 67 8 ®¯: scherrer0? 80 ¨p¾.. 1J K5 2J

(22) 8 L2? ü w/8 : ¾X +<<× <, , <g<L2 Ä) +D 2. 3. 3+. 21,22. o. Fig. 3. Excitation and emission spectrum of Y(2-x-y) O3 : Eux, Liy (x=0.06 mol, y=0.2 mol).. x=0.6534, y=0.3427) !... O : Eu , M (x=0.06 mol, y=0.2 mol)?!8 F Y 7 ç M ×"#5 $a %& ~Á.. g A +D L2-Á ÿ8 F7 ç M ×"# Fig. 3? ~Á.. M ×"# ¾X Be D F nD) 0 612 nm?! ' M ¬7: ~Á.. 1J K5 2J8 â8 (2-x-y). 3. x. 5. y. 7. 0. 2001, Vol. 45, No. 3. 2. 2. 3. 2. 23. 4.

(23) 240. !"#. Fig. 5. SEM photographs of Y(2-x-y)O3 : Eux, My (x=0.06 mol, y=0.2 mol) at 1100 oC Sr Ba.. . L2-Á ÿ 9&8 672 2 6µ 1 ¨ .. @ABC? 80 GHe /& n : 1100 C ?! + /Ü? 0 Å,n&è½é) ®ã e T: Fig. 5? ~Á.. ) e 45 9 &qD 2) EF 2 3 +: D4 ², g 3 +q8 $X5 ) 8 $³ E ! M ±8 ]c? OP ½5 ) U e.. ¼ DV± L2-3 ö5 Y O ? k0 1J K5 2J DV L2)¸ 9&q8 D 6Ý ®ã Á.. L2E3 ö5 Y O 8 9&67 100ý170 nm ±D, +D L2e o. 2. 3. 2. 3. none Li Na K Mg Ca . 5 300ý500 nm ±D, D D L2e 5 230ý300 nm±D, gD L2e 5 130ý170 nm±D, g+ , × g+ D L2e 5 60ý100 nm ±I.. âDV L2 é»2 £ 9&/¶: ², NÐ + L28 é»? 9&2 6µ EI², , × g+ D L2e é»? 9&8 D 7G-Á.. D_ èr5 U âDVq L2 é » n 8 /0 ?! L2e â8 ùÆîD - DD 8G) 4'EF 9& ? OP ½\ ) Ue.. ! ÇZD 5 ùÆî D - 1J DVD L2-X 9&8 ? 6µ Journal of the Korean Chemical Society.

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(25) . OP ½\², 2J DVD L2-X 5 ÇZ i ùÆî8 /0V±2 p! 9&? OP ½\3 öi 9&8 -0 ) #°e. . NÐ ùÆ+D 9 é»2 g OPD :;D , 100 nm±8 9&2 300 nmÑ3 <; ®ã Á.. M± +=, >, >g, L2>× Ä) 672 !.. D >! ?Ô jD L2 Y O : Eu8 M¬72 45 5 @ABC) GHe 2 100 nm ±) 9& 672 º» 47 ÿ D², 1J K5 2J DVD L2-X, $XT %) 9& ?± ±@ A)¸ 8 ±: «2%B. Ue.. 2. 3. â DVqD n ~? ´µ /¶·)¸ 5 V±?!± BD 21E, 9& 672 4², £ 9&: ¹ @ABC D'EF Y O : Eu : GHEI², 1J K5 2J DV L2EF /Ü8 9& MN? ® Ce OP H,EI.. 1J K5 2J DVD L2e Y O j5 9- H: 23², F7 ç M %&± é P ~Á.. H )3 öÝ ¨ Á.. ¼ DV± L2-3 ö5 Y O ? k 0 1J K5 2J DV L2)¸ 9&8 D Á e 9&q5 D4Á.. 1J8 DVq L2EI ÿ2 2J DVq L2EI ÿ ¾. 9&2 6µ EI², N± ¦ µ !.. NÐ, 1J8 DVq A?! +DV L 2D ÿ? 9&672 300ý500 nm) 9&D 2 :;Eµ !², 2 2 M¬78 Pr ~Á.. @ ABC D'EF Y O : Eu : GH. ÿ + DV L2EF B /Üq5 PL CL í T? 8EX "# $% &' ( ) ,' D 21 ) ¾.. 2. 3. 2. 3. 2. 2. 3. 1. R. O. Petersen Proc. IDW'96 1996, 2, 17. 2001, Vol. 45, No. 3. 3. Y2O3 : Eu. . 241. 2. Vecht, A.; Jing, X.; Gibbons, C.; Ireland, T.; Davies, D.; Marsh, P.; Newport, A. SID Tech. Dig. 1998, 29, 1043. 3. Jiang, Y. D.; Wang, Z. L.; Zhang, F.; Paris, H. G.; Summers, C. J. J Mater. Res. 1998, 13, 2950. 4. Pauling, L. Z. Krist. 1930, 75, 128. 5. Wyckoff, R. W. G. Crystal Structures; Interscience Publishers Inc.: New York, 1965. 6. Mandel, M. Appl. Phys. Letters. 1963, 2, 197. 7. Toma, S. Z.; Palumbo, D. T. J. Electrochem. Soc. 1968, 115, 64C. 8. Blasse, G.; Bril. A. Philips. Tech. Rev. 1970, 31, 304. 9. Weber. M. J. Phys. Rev. 1968, 171, 283. 10. Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, A. W.; Kaldor, A.; Louie, S. G. ; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704. 11. Nanophase Materials: Synthesis-properties-Applications; Hadjipanayis, G. C., Siegel, R. W., Eds.; NATO ASI Series E, 1993, vol. 260. 12. Li, Z.; Hahn, H.; Siegel, R. W. Mater. Lett. 1988, 6, 342. 13. Gleiter, H. Prog. Mater. Sci. 1989, 33, 223. 14. Hase, T.; Kano, T.; Nakazawa, E.; Yamamoto. H. Adv. Electron, Electron Phys. 1990, 271. 15. Pechini, M. P. Method of Preparing Lead and Alkaline Earth Titanates and Niobates and Coating Method Using the Same to Form a Capacitor. U.S. Pat. No. 3330697, 1967. 16. Eror, N. G.; Anderson, H. U. Polymeric Precursor Synthesis of Ceramic Materials; Brinker, C. J., Clark, D. E., Ulrich, D. R., Eds; Materials Research Society: Pittsburgh, PA, 1986; p 571. 17. Morgan, P. E. D.; Bump, H. A.; Pugar, E. A.; Ratto, J. J. Oxy-Alkoxy Polymer Networks; Hench, L. L., Ulrich, D. R., Eds.; Wiley Interscience: New York, 1986; p 327. 18. Anderson, H. U.; Pennell, M. J.; Guha, J. P. Polymeric Synthesis of Lead Magnesium Niobate Powders; Messing, G. L., Mazdiyasni, K. S., McCauley, J. W., Haber, R. A., Eds.; American Ceramic Society: Westerville, OH, 1987; p 91. 19. Lessing, P. A. Am. Ceram. Soc. Bull. 1989, 68(5), 1002. 20. Kakihana, M. J. Sol-Gel Sci. Technol. 1996, 6, 7. 21. Chang. N. C. Appl. Phys. 1963, 34(12), 3500. 22. Wickersheim, K. A.; Leferer, R. A. J. Electrochem. Soc. 1964, 111(1), 47. 23. Cullity, B. D. Elements of X-Ray Diffraction, 2nd edn.; Addisson-Wesley: Reading, MA, 1978; p 96..

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Synthesis of Y O :Eu Added the Group 1 or 2 Elements Using Complex-Polymerization and its Luminescent Properties  O :Eu 1, 2 Y

Synthesis of Y O :Eu Added the Group 1 or 2 Elements Using Complex-Polymerization and its Luminescent Properties O :Eu 1, 2 Y