Pr3+ doped SrAl2O4:Eu2+,Dy3+ phosphor was synthesized by combustion method. X-ray diffraction showed the samples had a monoclinic crystal structure. Emission spectra showed a peak at 515nm under 365nm excitation. Decay curves showed the initial intensity was three times higher with Pr3+ doping. Scanning electron microscopy images showed Pr3+ doping resulted in uniform grain sizes in the solid solution.

1. 24 º 4 ¼ × ³ Vol.24 No.4
2010 «8¸ CHINESE JOURNAL OF MATERIALS RESEARCH August 2 0 1 0
Pr3+Ü · SrAl2O4 : Eu2+ ¢ 3+
Dy § §
° ß ´ ∗
»· ¡ Ð ØÎ Ð ­ 710021)
ÈÐ Á
Ü
¸²
(
Ç Ç Pr ¿Ú SrAl O : Eu £Dy
3+
À± , Ø´ Pr ¿ À ªÚ Æ ¥ È
2+ 3+ 3+
Ú Â SrAl O ¸ Ï
2 4
, ¯À ÌÀ Ì , ´ ¹ 515 nm, Û À ´ 320 nm
¤­
, 2 4
Ï 360 nm ÚÌ ¥ ¿ Pr ÆÄ ½¼Ú 3+
££Ú Æ ¬µ· ¿ Ú 3 ¥
¢© ¹©
,
Ý Ø ×½ , Ç , SrAl O , Ö ¿, À½ 2 4
O482, O614 Ø 1005-3093(2010)04-0343-05
Effect of Pr3+ on Luminescent Properties of SrAl2 O4 : Eu2+ ,
Dy3+ Phosphor Prepared by Combustion Synthesis
FAN Guodong∗∗ XIAO Guoping
(Key laboratory of Auxiliary Chemistry & technology for Chemical Industry,
Ministry of Education, Shaanxi university of Science & technology, Xi an Shanxi 710021)
* Supported by Scientific and technological project in Shaanxi Province No.2008K07-32.
Manuscript received May 5, 2010; in revised form May 26, 2010.
** To whom correspondence should be addressed, Tel:(029)86168933, E–mail: fangd@sust.edu.cn
¨
ABSTRACT Pr3+ doped SrAl2 O4 Eu2+ , Dy3+ phosphor was synthesized by combustion method.
The modification of optical properties of the sample has been investigated. X-ray diffraction pattern
indicates that the samples possess a monoclinic crystal structure. The emission spectra shows a continuous
luminescence band with a peak at 515nm and excitation spectra shows two peaks at 320 and 360 nm. The
decay curves show that the initial intensity is three times before doping praseodymium. The morphology
shows praseodymium has a great role in formating uniform grain size solid solution in SrAl2 O4 : Eu2+ ,
Dy3+ , Pr3+ phosphor.
KEY WORDS inorganic non-metallic materials, combustion, SrAl2 O4 , Pr3+ doping, luminous materials
À Þ Î °ÛØ­ §
¼ , È¿¢ µÊ ÝÆ ¤ §Æ ¼ Æ
Ê Á ¨ §§Á ؼ , ¬ ±È Î
[1] [2] [3,4]
¤
¼ , ´ ¤ ¼ ¤² » º Á Æ Æ ¨ Ð ¢Ô
´Î : ¢ Ö ÙÒØ Ö ¼ ¤Ð ÆÎ Ø º », Ä © ¶,
, § ZnS : Cu, Co ´ © ¢ ÙÒ ¹ © Ë Ä² Ø , ¨
ب Ð¢Ô , § SrAl2O4 : Eu, Dy ´ ¤ [5]
¤ Æ [6−12]
, Ʋ½ Æ Æ
¼ Ø ´«Î § Ì °¤ Æ ¬Ê, ¬ Ô ¬Ø
¼ Ø 10 §Å, ¶· Ï Ì Ò» Ôº« , ÇØ Ï ¶ Á ¬¤¸ ¬¿
Î ¨, Ü Ø¬ ² ¤ ¢ Ý ,
 ǥ 2008K07-32 Ï ÑØ´ Í × Â ½¨¹ÃÐ¢Ó §Ý Æ [13] ¤
Ç¥¥
*
– Æ Æ Sr3Al2O6 : Eu2+ Pr3+
¬ 5 ¹ 5 ÓÕƼª2010 ¬ 5 ¹ 26 ÓÕ º¼¥ , Pr3+ Ø¥ » Sr3 Al2O6 : Eu2+ Ø
½Ê
2010
: ƨ, Ô
¨ [14] ¤ ¼ Æ Pr3+ ½Ø SrAl2 O4 :

2. 344 ¼ × ³ 24º
Eu2+ 3+ , × ³ Pr3+ ½Æ ¨Ø Ä ¤ c=0.516 nm, β=93.415◦ , Ø ´ SrAl2 O4
±¡
Dy
ÎÁ, ÍÍ, Ö Î ¤£ ¥ Pr3+ Ø ½
Ï, SrAl2O4 ¸ 28.4◦ Î 29.9◦ ËØÙʳ ß, È
1
¯ ¢Ï ¾ ÎØ Al(NO3)3·9H2O Ï SrAl4O7 ØÆ ÙÊ³Í Ç ¤
Sr(NO3 )2 H3 BO3 H2 NCONH2 Eu2 O3 (4N) Pr3+ Ø ½Ï x=0.17% 600 § ¬,
Dy2 O3 (4N) Î Pr4 O7 (4N), Ê H3 BO3 Ø¡ Ç ÃØ ¤ 1 § Ç, ½
ÌÏ´ 3%, ­ É¢ÔØ¡ ´ 7 : 1, Pr3+ Ø ° Û ¹ ¼ Ø ¤ «,
½Ï x ´ 0 0.13% 0.17% 0.23% Î 0.30%¤ Æ Æ SrAl2 O4 : Eu2+ Dy3+ ¼ , ½
Æ ß Ï É¢ ¡, Æ É¢ Ó ÏØ Pr3+ SrAl2 O4 Î Á, ÈÏÕÉÏ
ɢР­ Î ¢Ñ ° 80 §ÏÇ 30 min ½¼Ç ½Á ¤
Æ ¢Ì ¡¤ÆÎÌ ¡Ñ 80 §ÏÇ 1 Ç SrAl2 O4 Ø 5 ¿ Ùʳ (011)
2 h, »¯« ¡, Æ ß Ð Ò (−211) (221) (211) (031) Ø ÄÂ Ý ¼ ¤
¡¤ 600 §Ö¶ ʤ ¤ ß Ø , ¡
Ø ¤ µ 3–4 min È
° ( ß ª ° «°), ¹ Ø ß ³ ¬
«, Æ Ø ¼ Ø Ä¼´¦Ü ¤
ª ¦ ³
Ç ÏØ 2.2 Pr3+ SrAl2 O4 : Eu2+ Dy3+ Ú
Þ
¦ ¬
Ç Ô Û, ° Ç ÏØ , ¿ ÆÉ ½ Pr3+ ² ØÙ ¤·
ߧ± ¤ Æ Ú ×ÔÑÓ
2
º Ø ½ Pr Ù
3+
´Þ³¶´«ÁÒ, ½ Pr3+
¢ , ¾Ç ° × ß× Pr3+ ¸ 360 nm س ´, ¸ 320 nm Ø
½Ø SrAl2 O4 : Eu2+ Dy3+ ° ¤ ³ ¦ , »º Á Æ Ø µ ¤Á
D/max2200PC X Ê Ù Ê¥ Matsuzawa Ý [15]
»º Á Ø SrAl2 O4 :
Ø , CuKα µÊ, Ó´ 40 kV, ´
20 mA ¤ FluoroMax–4 Æ «¢ (Ù
´´ÑÛ) Ñ ØÙ Ê Î Ü
©» , Quanta250 FEG Þ ² ±
ز ٤
ƨ¶
Æ£Þ
2
³
2.1 Pr3+
1 µ ¥ØÑ É Pr3+
SrAl2 O4 : Eu2+ Dy3+
Á
Ú
SrAl2 O4 , º SrAl4O7 ½Á ¤ Pr Ø¥ ,
¤ 3+
Ñ Ê SrAl4 O7 Á¸ 31.2 Ë ÝØÆ ÙʳÏ
◦
­© , SrAl2 O4 Á Ø Ù Ê³ ´¤Ò Pr3+ Ø 1 ¶ Pr3+ ¾ Ù Ù XRD
½Ï x=0.17% , SrAl4O7 ØÆ ÙÊ³Ê , ÙÊ Fig.1 X–ray diffraction patterns of samples doped
SrAl2 O4 Ø PDF ¿ (34–0379) Æ¬Ø with different Pr3+ additive (a) 0; (b) 0.13%;
¾ , ½ Û´ a=0.84424 nm; b=0.8822 nm; (c) 0.17%; (d) 0.23%; (e) 0.30%
Ù1 ¶ Pr3+ ¾ Ù ÅÃ
Table 1 Crystallite size of samples doped with different Pr3+ additive
Crystallite size/nm the average crystallite
Number
D011 D−211 D220 D211 D031 size/nm
1 30.5 25.4 37.9 27.4 26.5 29.5
2 31.3 28.5 35.4 26.8 25.4 29.5
3 33.0 29.1 30.8 32.1 26.9 29.5
4 33.0 29.1 31.9 28.7 26.3 29.8
5 33.7 30.4 34.6 32.6 26.6 31.6

3. 4 ŧÞ:Pr 3+
¾¯ SrAl O2 4 ¡
: Eu2+ Dy3+ ©Ù Å 345
2 ÙÚ 4 ٠ݪ¼À
Fig.2 Exission spectra of samples (a) samples doped
Fig.4 Decay curves of samples (a) samples doped
without Pr3+ additive;
without Pr3+ additive; (b) amples doped with
Pr3+ additive
× Ø ´, 4f6 5d→4f7 © ¨ §¾Ï­
Ë, Õ Eu2+ ° Ø 5d ÃÖÕÔ °Ø
ÄÜ´ÖÍ, ¥ÅÖÈ ½Øµº ¦ 4f65d Ñ
Âب ´Ë ب , Ù Î
Ê ØÆ ¤ Ø Ê·Ç
Eu Ø Æ
3+
³, ÆÉ Ê Eu ¦ ±
3+
¿ ³´ Eu
« ³
2.3 Pr
Þ
3+
2+[18,19]
¤
SrAl2 O4 : Eu2+ 3+
Dy Ú ¦ µ
4 § Ç, ½ Pr3+ Ø §
Ù Ë
µ ½ Pr Ø Á µ , Ð Ü©É Ê ½
3
3+
Fig.3 Emission spectra of samples (b) samples doped
3+
with Pr additive
Pr3+ Ø « µ ½ Pr3+ ØÍ ( µ
3 )¤ §¾» Ê ¨ ÊØ Û
2+
Eu , Dy ,3+
Ù ¢¿ ³ Ë , ÏÝ Ù ©¨ Ø¡Ò, ´«¾» ¨
³ ¸ 365 nm, ³ ¸ 270 330 nm¤ ÊØ ¸ §§ Ù ©¨ Ø¡Ò¤
Æ , ³Ø ¸ Å ¤ 5 ¿ nm, ¨ Æ Í© ¨ Ø ³ , « ½Ø µ
ص ¦Ã¤ ¨ Ø ³ ¦µ ¤ §Î ´«
3 ¦ ¾ 360 nm ³ Ù Ø Ê ÒØ¨Ï ¤¤ IJةË, ¦Ç¨Ø
¤ Ø Ê ³ ¸ 515 nm, · ¥ÓÃ Ø , « »Ø¨Ï Ù ¤×
Æ ¤ »º Á Ø SrAl2O4 : Eu2+, ¢¢ØÙ Ê Ø¨Ï, Ø «
Dy3+
Æ Ø
Ê (³ ¸ Å 520 nm) ,
§ ­, ÄÂ Ë, ² ¸
Ê »¤
¥ ³
³ ¸ Å È ­³ È ¤¦¤ ³« ¨ , 2.4 Pr3+ SrAl2 O4 : Eu2+ Dy3+ Ú
Þ
¦
60–90 nm ¤Ë ÄØÏ Â Ì ¬Óè , µ ½ Pr3+ Ø , Æ ¢ Û
³Ø¸Å ¤¤ Ä ( 5a); ½ Pr Ø 3+
«ÍÍ,
ØÙ Î Ê , ´ ¢Á ( 5b) ¤ Í Ç XRD Ø
Ø Eu2+ Ê Ø 4f6 5d–4f7 ¶± [16] , ¢Ã¤Ð Ä Ëµ¼», ¨ Æ Ä
Ravichandran Ý [17] ² ³ SrAl2 O4 : Eu2+ ¶¤ ¶Ø , ¨ ÄØ Ý¨µ¼
Dy 3+
¼ Ø Ê ¾ ¤ ¤ 4f–5d » £Í È ÝŠت ¦Ã¤

4. 346 ¼ × ³ 24 º
5 Ù³ Ú
Fig.5 SEM morphologies of the samples (a) samples doped without Pr3+ additive; (b) samples doped
Æ
with Pr3+ additive
the SrAl2 O4 :Eu, Dy Phosphor, Jounal of Hebei Univer-
3 sity(Natural Science Edition), 21(4), 443(2001)
Æ ½ SrAl2O4 : Eu2+,
Æ Ý , Ñ£ÔÒÕ ½ Ø ´, ÑÑ
Ñ
( , (
Pr3+
), 21(4), 443(2001))
Dy3+ ¼ , Pr3+ ½
«ÍÍØ ¢ Á
5 WU Xiulan, REN Qiang, DONG Wendie, Combustion
¤Ò ½ Pr3+ Ø¡ synthesis and properties study of SrAl2 O4 : Eu2+ , Dy3+
Û ´ 0.17% , Ø ´( Î ) Á phosphor material, China Ceramics, 40(6), 13(2004)
µ, ¥»¡, Ç £
SrAl2 O4 ¤ Ø Ê Ë , ³ ¸
SrAl2 O4 : Eu2+ Dy3+
À½ Þ ªØ´, ËÆ­
( ,
, 40(6), 13(2004))
515 nm, Ù ³ 320 360 nm ØË 6 GUO Shaohua, Study on Synthesis of Ultrafine Luminous
, Û ½ Pr Ø SrAl2O4 : Eu2+ Dy3+ Ø
À ¾½Ç ¿É
3+ Powder by Combustion Method, Master thesis, Beijing,
¢Ã¤ ÊØ Eu2+ ÙÒ Î Ê , Beijing Institute of Technology(2004)
ÄÉ Ñ¹Ô½,
Dy3+ Î Pr3+ · ÙÒ , ´ ¢Ì ( ,
Ñ
, ,
«¤Pr ½ÆÐ ¢ ÓØ
(2004))
» §Û 7 S Ekambaram, M Maaza, Combustion synthesis and
§ Ø Ä, Ð »Ð ¢ ÓØÅ «, luminescent properties of Eu3+ –activated cheap red
µ · ½ Ø3 ¤
¯
phosphors, Journal of Alloys and Compounds, 395(1),
132(2005)
Û 8 CHEN Ren, Modification on Luminescent Properties of
SrAl2 O4 : Eu2+ , Dy3+ phosphors by lanthanon Ions Dop-
1 ZHANG Zhongtai, ZHANG Feng, SUN Hongfei, Prop-
ing, Master thesis, Guangdong, GuangDong University of
erties and luminescent mechanism of SrAl2 O4 :Eu, Dy,
Technology, (2008)
a long-lasting phosphorescent ceramics, Journal of Func-
¿ £
SrAl2 O4 : Eu2+ Dy3+
À½ À ªÚ Æ, ѹԽ, Á¤, Á¤ Ñ
( ,
tional Materials, 30(3), 295(1999)
( ˨, ², « , ¥ , À­ SrAl2 O4 :
Eu, Dy Ú ªÞ ÀØ ª½
, , 30(3), 295(1999))
9
(2008))
J Bang, M Abboudi, B Abrams, P.H.Holloway, Combus-
2 LIN Yuanhua, ZHANG Zhongtai, CHEN Qingming,
TANG Zilong, GONG Jianghong, A study on preparation tion synthesis of Eu-, Tb-and Tm- doped Ln2 O2 S (Ln=Y,
of long afterglow photoluminescence glass and its proper- La, Gd) phosphors, J. Lumin., 106(2), 177(2004)
ties, Material Science and Technology, 8(1), 1(2000) 10 PENG Tianyou, YANG Huangping, PU Xuli, HU Bin,
± , Ë ¨, ¸ , « , ¯ , ÀÄ À²É JIANG Zucheng, YAN Chunhua, Combustion synthesis
ÚÇ Þ ªØ´, ½ Ñ ¨, 8(1), 1(2000))
(
and photoluminescentce of SrAl2 O4 : Eu,Dy phosphor
3 YUAN Ying, LI Xueshen, PU Hongting, SHI Huisheng, nanopaticles, Materials Letter, 58(2), 352(2004)
Study on the luminescent properties of long-life afterglow 11 WU Guoyuan, BAO Lijun, YANG Yu, Study on the
fluorescent coatengs based on stronium europoum alumi- preparation of green aluminate long afterglow phospho-
nates, Paint & Coatings Industry, 7, 8(1998) rescent materials used the method of combustion, Journal
² ­, ÑÏ, Ð , Ñ£ÔÒ ¯À of Functional Materials, 35(sl), 217(2004)
Ú À ªÚØ´, Ʊ, À¾, Ý , £¹ Ç Ç Ñ£Õ À½
( ,
, 7, 8(1998))
ÚØ´, ª½ , 35(sl), 217(2004))
(
4 LIU Zhen, YANG Zhiping, Study on Long-Afterglow of

5. 4 ŧÞ:Pr 3+
¾¯ SrAl O 2 4 ¡
: Eu2+ Dy3+ ©Ù Å 347
û
12 CHANG Suling, HAN Yongjian, CAO Lixin, Effect of 16 SUN Jiayue, DU Haiyan, Solid Luminescence Materials,
¥¤·, ªÊÚ, Ñ È Í, 2003)
H3 BO3 flux on luminescent properties of SrAl2 O4 : Eu, (Beijing, China Chemistry Press, 2003) p.545
Dy prepared by combustion synthesis, Nonferrous Metals, ( ,( ,
60(3), 26(2008)
, Ë ¬, ¿Ã , H BO Ç Ç SrAl O
p.545)
Eu, Dy À ªÚ Æ, À ×, 60(3), 26(2008))
( 3 3 2 4 : 17 D Ravichandran, S.T Johnson, S Erdei, R Roy, W.B
White, Crystal chemistry and luminescence of the Eu2+
13 CHEN Yicheng, CHEN Dengming, ZHAN Yansong, Mod- activated alkaline earth aluminate phosphors, Displays,
ification of afterglow properties of SrAl2 O4 : Eu, Dy phos- 19(4), 197(1999)
phors by impurity doping, Jounal of the Chinese Rare 18 E Zych, D Hreniak, and W Strek. Spectroscopic prop-
Earth Society, 19(6), 502(2001) erties of Lu2 O3 /Eu3+ nanocrystalline powders and sin-
£À, Ü , , ¿ÉÚ ¦ Eu2+ , tered ceramics, Journal of Physical Chemistry, 106(15),
À¯ ÚºÄ, ËÆ Ñ
( SrAl2 O4 :
Dy3+ , 19(6), 502(2001)) 3805(2002)
14 LIU Lan, Study on red long afterglow phosphors of 19 GUO Hai, it Investigation of upconversion in rare earth
Sr3 Al2 O6 co-activated by Eu2+ and Pr3+ , Master thesis, ions doped nanosized (ultrafine) oxides and functional rare
¦
º ÆÄ ´Î¼Ì¿Ô½ ÊÆ ÅÁÍ Ñ ÙËÆÄÊ Å
Tianjin: Tianjin university(2007) earth oxide film, Ph D thesis, An hui, University of Sci-
Ð, £ ÛÓ Sr Al O × À À½
É Ñ¹ ËÆ Ñ
Eu2+ Pr3+
ÚØ´, ѹԽ, , Ñ (2007))
( ence and Technology of China(2005)
Ä Ê,
3 2 6
(
15 T Matsrzawa, Y Aoki, N Takeuchi, A new long phospho- , , , (2005))
rescent phosphor with high brightness SrAl2 O4 : Eu Dy, £
The Electrochem Society, 143(8), 2670(1996)