Mn 2+ 8 ý ] K ¤S ë s; c  \ ¥ Zn 2−x SiO 4 :Mn 2+ x : g à k Ä ] k ù° Ë Ñ= k8 ý ] k ù° Ë Ñ ¤V R Ë
» ò 6 B £
@ / < Æ § o < Æõ , Â Òí ß 617-736
T
) ç ¬ £ ∗
@ / < Æ § F « Ñ/ B N < Æõ , Â Òí ß 617-736 (2007¸ 12 Z 4 24{ 9 ~ Ã Î6 £ §)
Zn
2−xSiO
4:Mn
2+x[ j b + þ AF g ^ \ ¦ ¦ © ì ø Í6 £ xZ O ` ¦ s 6 x # ] j % i Ü ¼ 9, Mn
2+_ < Ê| ¾ Ó\ É r
& ñ ½ ¨ ¸ü < & ñ $ í , + þ AF g: £ ¤$ í ` ¦ ì r$ 3 % i . X- r] X z ´+ « > õ \ ¦ : x # Zn
2−xSiO
4:Mn
2+x[ j b
s (113) x 9 (410) ~ ½ Ó ¾ Ó_ Å Ò & ñ ` ¦ t 9, (220), (223), Õ ªo ¦ (110) x ß ¼\ ¦ t H & ñ
© Ü ¼ Ð $ í © % i 6 £ §` ¦ S X ½ + É Ã º e % 3 . Mn
2+_ < Ê| ¾ Ós 0.005 mol\ " f 0.03 mol Ð 7 £ x < Ê\ { 9
[ þ t s ç H{ 9 K t 9 ß ¼l ¸ 7 £ x < Ê` ¦ · ú Ã º e % 3 Ü ¼ 9, Zn
2−xSiO
4:Mn
2+x[ j b _ + þ AF g Û ¼& 7 à Ô! 3 É r Mn
2+_ < Ê| ¾ Ós 0.03 mol\ " f © a % ~ É r : £ ¤$ í ` ¦ f ` ¦ · ú Ã º e % 3 . Mn
2+_ < Ê| ¾ Ós 0.03 mol t 7
£
x < Ê\ + þ AF g y © ¸_ 7 £ x H X <, s Qô Ç & ³ © É r Mn
2+_ < Ê| ¾ Ós 7 £ x < Ê\ & ñ $ í _ ¾ Ó ©
÷
r ë ß m { 9 [ þ t _ ß ¼l x 9 ³ ð + þ A © _ o\ _ ô Ç כ e ` ¦ · ú Ã º e % 3 .
PACS numbers: 78.55.-m, 78.20.-e
Keywords: Zn
2SiO
4:Mn
2+, + þ AF g ^ [ j b , F g µ 1 Ï F g
I. " e  ] Ø
¨ î
ó ø Í J V , + þ A n Û ¼e ¦ Y Us (flat panel display: FPD) H
© 6 x o÷ & ¦ e t ë ß n Û ¼e ¦ Y Us è H @ / & h oü < ¦ 6 f
¸ o x 9 $ § 4 è ¸\ ¦ 9 כ ¹ Ð ô Ç . 8 Z } É r ´ òÖ ¦ _ n Û ¼ e
¦ Y Us \ ¦ > hµ 1 Ï l 0 Aô Ç ½ ¨ ' × æ X < plasma dis- play panel (PDP) ì r \ ¦ q 2 © # , f t H PDP ë ß
p
u © 6 x o÷ &t H 3 l wÙ þ ¡t ë ß # Q t © & h ` ¦ כ Ü ¼
Ð ¨ î ÷ & H electro-luminescence display (ELD) x 9 field emission display (FED), light emitting diode (LED) 1 p x s
e . FEDü < PDP ° ú É r @ /³ ð& h ¨ î ó ø Í n Û ¼e ¦ Y Us
è \ H Á º% Á Ð Z } É r ´ òÖ ¦` ¦ ° ú H + þ AF gÓ ü t| 9 [ þ t _ > h µ
1 Ïs כ ¹½ ¨ ) a [1–5]. s Qô Ç ¦´ òÖ ¦ _ + þ AF g ^ > hµ 1 Ï` ¦ 0 A K
Ð $ + þ AF g ^ _ µ 1 Ï F g B j& m 7 £ §` ¦ µ 1 ßy H כ s B Ä
º × æ כ ¹ . Õ ª s Ä » H & ³F > hµ 1 Ï ) a + þ AF g ^ _ ¦& ñ Ã º ë
ß ` ¦ or & " f % 3 ` ¦ Ã º e H 6 f ¸\ H Õ ª Ã º - Á
º ¸ ´ ú §Ü ¼ 9, ¢ ¸ ¦& ñ à º[ þ t _ > h $ í s \ O # Q" f 6 f ¸
¾ Ó © _ ô Ç> e l M :ë H s . s Ð H y $ í ì r _ F g
< Æ& h % i ½ + É` ¦ µ 1 ß) " f, Õ ª % i ½ + É_ F G @ / o\ ¦ : x K 6 f ¸\ ¦ 7
£
x r v H ½ ¨ × æd s ÷ &# Q ë ß ô Ç [6]. : r ½ ¨
∗
E-mail: [email protected]
\
" f H Zn 2 SiO 4 \ ¦ ¸^ (host) Ð # Mn 2+ \ ¦ Ö ¸$ í ^ (activator) Ð ' # 0 l qÒ o + þ AF g ^ Ð 6 x l 0 A # Mn 2+ _ < Ê| ¾ Ó\ [ j b ` ¦ ] j ¸ % i Ü ¼ 9, [ j b _
& ñ ½ ¨ ¸, ³ ð ½ ¨ ¸ Õ ªo ¦ + þ AF g Û ¼& 7 à Ô! 3 ` ¦ 8 £ ¤& ñ
¦ [ j b _ & ñ $ í x 9 ³ ð + þ A © õ + þ AF g ´ òÖ ¦ õ _ ' a >
\
@ / # ½ ¨ % i .
II. ÷ m Ç ] M ö
Zn 2 SiO 4 :Mn 2+ ì r ´ ú r « Ñ H Mn 2+ _ < Ê| ¾ Ó` ¦ 0.005, 0.01, 0.03, Õ ªo ¦ 0.05 mol Ð or v 9, ZnO (99.9
%), SiO 2 (99.9 %) Õ ªo ¦ MnO (99.99 %)_ o < Æ& h | ¾ ÓÜ ¼
ÐÂ Ò' ï r q ÷ &% 3 . Zn 2 SiO 4 :Mn 2+ [ j b _ ] j ¸ H Ä º
1 Ball mill` ¦ l 0 A # e ¦ Û ¼h Ë : ÐÖ ¦ (Bowl) \ ï
r q ô Ç r « Ñü < ZrO ^ ¦` ¦ ° ú s V , # Q 460 rpmÜ ¼ Ð 20 r
ç ß Ball mill` ¦ ô Ç Ê ê D ¥ ½ + Ëô Ç ì r ´ ú _ ^ ¦` ¦ Q? /# Q |
¸ % i . | ¸ ) a r « Ñ\ ¦ [ j b ¸m \ V , ¦ l Ð
\
" f 3 ◦ C/min _ q Ö ¦ Ð 600 ◦ C \ " f 4 r ç ß 1 l x î ß è
(Calcining)/ B N& ñ ` ¦ 2 ; Ê ê 2 Ball mill` ¦ % i . 2
Ball mill s = å Q è ß ì r ´ ú \ ½ + Ë] j (Binder: PVA(polyvinyl-
Alcohol), 4 wt.%)\ ¦ ' # · ú » ¡ ¤$ í + þ A~ ½ Ód ` ¦ s 6 x K ì r
-518-
Fig. 1. XRD patterns of Zn 2 SiO 4 :Mn 2+ ceramics with different Mn 2+ ion concentrations.
´ ú
` ¦ $ í + þ A % i . $ í + þ A ) a : \ Ï @ (pallet)` ¦ l Ð\ V , ¦ 1200 ◦ C \ " f 4r ç ß 1 l x î ß è % i .
Zn 2 SiO 4 :Mn 2+ [ j b _ & ñ ½ ¨ ¸ü < & ñ $ í ` ¦ ¸ l
0 AK X- r] X (XRD, X-ray diffraction)` ¦ 8 £ ¤& ñ % i Ü
¼ 9, X- _ í ß ê ø Íy (2θ) É r 10 ◦ ∼ 80 ◦ % ò % i \ " f ì r { © 0.02 ◦ _ Û ¼ ± p 5 Å q ¸ Ð 8 £ ¤& ñ % i . ³ ð p [ j½ ¨ ¸ H Å
Ò & ³p â (scanning electron microscope : SEM)` ¦ s 6
x # 8 £ ¤& ñ % i Ü ¼ 9, + þ AF g Û ¼& 7 à Ô! 3 É r 254 nm _ Å Ò ) a
ü @ © ` ¦ ° ú H Xenon Ï þ á Ô\ ¦ F g " é ¶ Ü ¼ Ð H + þ AF g F
g ¸> (Perkin-Elmer, LS50B)\ ¦ 6 x # z ´ : r \ " f 8 £ ¤
&
ñ % i . # l F g Ü ¼ Ð H Zn 2 SiO 4 :Mn 2+ [ j b \ " f f ¨ Ã
º y © > H 261 nm _ © ` ¦ s 6 x % i .
III. ÷ m Ç] M ö+ s ÇÊ Ý õ m Í w ² o
Fig. 1 É r Mn 2+ _ < Ê| ¾ Ó 0.005, 0.01, 0.03, Õ ªo ¦ 0.05 mol \ É r Zn 2 SiO 4 :Mn 2+ [ j b _ r] X © ` ¦ Zn 2 SiO 4 ì
r ´ ú _ JCPDS (37-1585) õ ü < q §ô Ç XRD õ s
. Mn 2+ _ < Ê| ¾ Ó\ ' a > \ O s ¸ H [ j b É r JCPDS \ ]
jr ) a r] X © õ ¸ ú { 9 u % i Ü ¼ 9, (113) x 9 (410)_ Å Ò x
ß ¼\ ¦ t 9, (220), (223), Õ ªo ¦ (110) x ß ¼` ¦ t
H & ñ © Ü ¼ Ð $ í © % i . t ë ß , Mn 2+ _ < Ê| ¾ Ós 0.03 mol â Ä º (113) x 9 (410)~ ½ Ó ¾ ÓÜ ¼ Ð_ ~ ½ Ó ¾ Ó$ í s 8
&
t 9 (110) x ß ¼ : £ ¤Z > y 7 £ x < Ê` ¦ · ú Ã º e H X <, s
H Mn 2+ _ < Ê| ¾ Ós 0.03 mol Ð 7 £ x ½ + ÉÃ º2 ¤ ì r ´ ú _ & ñ
$ í
s ¾ Ó © ÷ & 9 : £ ¤ y (110) ~ ½ Ó ¾ ÓÜ ¼ Ð ´ ú § É r & ñ [ þ t s + þ A$ í
÷
&% 3 6 £ §` ¦ · ú Ã º e .
Fig. 2 H Zn 2 SiO 4 :Mn 2+ [ j b _ Mn 2+ < Ê| ¾ Ó (a) 0.005, (b) 0.01, (c) 0.03, Õ ªo ¦ (d) 0.05 mol\ É r
Fig. 2. SEM images of Zn 2 SiO 4 :Mn 2+ ceramics with Mn 2+ ion concentration.
& ñ + þ AI \ ¦ · ú Ðl 0 Aô Ç SEM s . Fig. 2(a), (b) _ â Ä º & ñ + þ AI ¦ Ô ¦ ½ ©g Ë :& h + þ AI \ ¦ s À Ò H ì
ø Í , (c)_ â Ä º & ñ + þ AI ½ ©g Ë :& h s 9, { 9 _ ß ¼l
ß ¼ 9 Ñ ü æ/ å J > $ í © % i 6 £ §` ¦ ^ ¦ Ã º e . (d)_ â Ä º
&
ñ _ ß ¼l H (a) ü < (b)\ q K ß ¼ Ô ¦ ½ ©g Ë :& h + þ A © ` ¦
f ` ¦ ^ ¦ Ã º e . + þ AF g ^ \ " f H { 9 â _ ß ¼l ß ¼ ¦ ¸
ª s Ñ ü æ/ å J 9 + þ AI ½ ©g Ë :& h { 9 Ã º2 ¤ G Ä ºl x 9 ¸ 7 £ x
# + þ AF g [ jl 7 £ x 9, ³ ð \ " f_ í ß ê ø Í\ _ ô Ç y n C _
< Hz ´s y è ) a ¦ · ú 94 R e . s כ É r { 9 _ â >
\
" f í S \ s { 9 # Q + þ AF g [ jl \ ¦ y èr v > ÷ & H X
< { 9 _ ß ¼l 7 £ x { 9 â > x 9 ¸ × ¦ # Q[ þ t # Q
© @ /& h Ü ¼ Ð Ä ºÃ ºô Ç + þ AF g` ¦ % 3 ` ¦ à º e l M :ë H s [7,8].
Fig. 3 (a) H Mn 2+ < Ê| ¾ Ó` ¦ ² ú o H Zn 2 SiO 4 :Mn 2+ [ j
b _ + þ AF g # l (photo-luminescence excitation) Û ¼& 7 à Ô
! 3
` ¦ · p כ s . + þ AF g # l Û ¼& 7 à Ô! 3 _ â Ä º Mn 2+ _
< Ê| ¾ Ós 7 £ x < Ê\ 200 nm\ " f 300 nm Ð V , É r % ò % i
\
" f # l (excitation) { 9 # Qz ` ¦ · ú Ã º e Ü ¼ 9 260 nm
H % \ " f þ j@ / ° ú כ` ¦ f ` ¦ · ú Ã º e . Mn 2+ _ < Ê| ¾ Ós 0.005 mol \ " f 0.03 mol Ð 7 £ x < Ê\ x ß ¼ ° ú כs 7 £ x
% i ¦, Mn 2+ _ < Ê| ¾ Ós 0.03 mol â Ä º, © H # l Û
¼& 7 à Ô! 3 s z ` ¦ · ú Ã º e . s כ É r Mn 2+ _ < Ê| ¾ Ó
\
É r & ñ ½ ¨ ¸ x 9 + þ A © _ o\ É r & ³ © Ü ¼ Ð Ò q ty
)
a . Fig. 3(b) H Mn 2+ < Ê| ¾ Ó\ É r Zn 2 SiO 4 :Mn 2+ [ j
b _ + þ AF g (photo-luminescence) Û ¼& 7 à Ô! 3 ` ¦ · p כ s
. Zn 2 SiO 4 :Mn 2+ [ j b _ + þ AF g Û ¼& 7 à Ô! 3 É r Mn 2+ _
< Ê| ¾ Ó\ ' a > \ O s Mn 2+ _ 4 T 1 → 6 A 1 s \ _ ô Ç 525 nm % ò % i H % \ " f µ 1 Ï F g x ß ¼ z ¤Ü ¼ 9 [9], Mn 2+ _
< Ê| ¾ Ós 0.005 mol\ " f 0.05 mol Ð 7 £ x ½ + ÉÃ º2 ¤ 519 nm \
"
f 526 nm Ð µ 1 Ï F g x ß ¼_ & h Ò o ¼ # s { 9 # Qz ` ¦ · ú Ã º e
% 3 H X < s õ H Û ¼ 2 ; § ¨ 8 © ñ 6 x \ _ ô Ç + þ AF g
Fig. 3. PLE, PL spectrum of Zn 2 SiO 4 :Mn 2+ ceramics with Mn 2+ ion concentration.
Fig. 4. A behavior of PL intensity and FWHM of (113) peak of Zn 2 SiO 4 :Mn 2+ ceramics with Mn 2+ ion concen- tration.
õ
H 7 Hë H _ ? /6 x õ ¸ ú { 9 u ô Ç [10]. Mn 2+ _ < Ê| ¾ Ó s
0.005 mol\ " f 0.03 mol Ð 7 £ x < Ê\ + þ AF g [ jl
7 £ x H X <, s כ É r Mn 2+ _ < Ê| ¾ Ós 0.03 mol Ð 7 £ x
½
+ É â Ä º & ñ $ í s ¾ Ó © | ¨ c ÷ r ë ß m (110)x ß ¼ ß ¼> 7
£
x H XRD õ ü < ' a t # Q Ò q ty K ^ ¦ Ã º e . [ j
b _ & ñ $ í s ¾ Ó © | ¨ c à º2 ¤ + þ AF g [ jl 7 £ x H X < s
H & ñ $ í s ¾ Ó © | ¨ c à º2 ¤ F g < Æ& h ;s S X Ò ¦ s 7 £ x ½ + É [11]
÷
r ë ß m & ñ $ í _ ¾ Ó © \ _ ô Ç Õ ªY U ß ¼l _ 7 £ x
\
_ ô Ç { 9 â > x 9 ³ ð \ " f_ í ß ê ø Ís y è÷ &l M :ë H s
[12]. + þ AF g _ ´ òÖ ¦` ¦ & ñ H × æ כ ¹ô Ç כ ¹ Ü ¼ Ð o
< Æ& h ½ ¨$ í , { 9 ß ¼l ü < C \ P Õ ªo ¦ { 9 ¸ ª _ þ j& h o
\
¦ [ þ t à º e [13]. " f Mn 2+ < Ê| ¾ Ó_ o\ { 9
& t ¦ ç H{ 9 ô Ç ½ ¨ ¸\ ¦ t H + þ AI 9, ß ¼
¦ ç H{ 9 ô Ç ½ ¨ ¸\ ¦ t H { 9 8 Z } É r { 9 Ø æ x 9 ¸ ü
@\ ¸ ³ ð \ " f_ í ß ê ø Ís y è÷ & H כ \ @ / # × æ כ ¹ ô
Ç כ ¹ Ü ¼ Ð 6 x ô Ç [14]. Õ ª QÙ ¼ Ð { 9 _ ß ¼l 7 £ x
" f { 9 s _ â > x 9 ¸ ± ú t H X <, { 9 â
>
H \ ¦ í S \ ¦ + þ AF g Û ¼& 7 à Ô! 3 _ µ 1 ßl \ ¦ y èr (
Ü ¼ Ð+ ì r ´ ú ? /\ " f Ò q t$ í ) a y n C` ¦ < Hz ´ H " é ¶ { 9 Ã º e
l M :ë H \ ± ú É r { 9 â > \ ¦ ° ú H ì r ´ ú { 9 à º2 ¤ Ä ºÃ ºô Ç + þ
AF g : £ ¤$ í ` ¦ · p H כ ` ¦ · ú Ã º e . ¢ ¸ô Ç, Mn 2+ _
< Ê| ¾ Ós 0.05 mol Ð 7 £ x < Ê\ + þ AF g Û ¼& 7 à Ô! 3 s y è
H s Ä » H 0 l x ¸ % 3 ] j (concentration quenching) & ³ © Ü
¼ Ð [ O " î ½ + É Ã º e [15,16].
Fig. 4 H Mn 2+ _ < Ê| ¾ Ó\ É r (113) x ß ¼_ ì ø Íu ; ¤ (full width half maximum: FWHM) õ + þ AF g [ jl _ © ' a
'
a > \ ¦ · p כ s . Å Ò x ß ¼ (113) x ß ¼_ ì ø Íu ; ¤ s y
è < Ê\ + þ AF g [ jl 7 £ x % i Ü ¼ 9, Mn 2+ 0.03 mol \ " f © a % ~ É r + þ AF g ´ òÖ ¦` ¦ Ðe ` ¦ S X ½ + É Ã º e .
s
כ É r ì ø Íu ; ¤ _ y è & ñ $ í _ 7 £ x \ ¦ _ p 9,
&
ñ $ í _ 7 £ x \ + þ AF g [ jl % i r 7 £ x < Ê` ¦ · ú Ã º e
.
IV. + s Ç Â ] Ø
: r ½ ¨\ " f H Zn 2 SiO 4 :Mn 2+ [ j b ` ¦ ¦ © ì ø Í6 £ xZ O Ü
¼ Ð ] j ¸ # Mn 2+ _ < Ê| ¾ Ó\ É r & ñ ½ ¨ ¸ü < ³ ð + þ
A © , Õ ªo ¦ + þ AF g: £ ¤$ í ` ¦ ì r$ 3 % i . & ñ ½ ¨ ¸\ ¦ · ú l
0 AK XRD\ ¦ 6 x # & ñ © ` ¦ ' a ¹ 1 Ï % i ¦, (113), (410), (220), (223), Õ ªo ¦ (110)x ß ¼\ ¦ t H & ñ
© Ü ¼ Ð $ í © % i 6 £ §` ¦ · ú Ã º e % 3 . ¢ ¸ô Ç Mn 2+ _ < Ê| ¾ Ó s
0.005\ " f 0.03 molÜ ¼ Ð 7 £ x < Ê\ [ j b _ p [
j½ ¨ ¸_ { 9 _ ß ¼l 7 £ x % i ¦, ç H{ 9 ô Ç & ñ $ í ` ¦
Ðe ` ¦ S X ½ + É Ã º e % 3 Ü ¼ 9, 0.05 mol\ " f H r { 9 _
ß ¼l y è 9 ç H{ 9 t 3 l w ô Ç { 9 ß ¼l \ ¦ ° ú H כ
`
¦ ^ ¦ Ã º e % 3 . + þ AF g Û ¼& 7 à Ô! 3 _ â Ä º Mn 2+ _ < Ê| ¾ Ós 0.03 mol{ 9 M : © a % ~ É r + þ AF g ´ òÖ ¦` ¦ Ð% i Ü ¼ 9, s H [ j
b _ & ñ $ í õ { 9 _ ß ¼l x 9 { 9 + þ A © _ > h \
É
r ? /Â Ò ì ø Í \ _ ô Ç y n C_ < Hz ´s y è > ÷ &# Q + þ AF g ´ ò
Ö
¦ s ¾ Ó © H d` ¦ S X ½ + É Ã º e % 3 . s Qô Ç ½ ¨ õ \ ¦ :
x K Zn 2 SiO 4 :Mn 2+ [ j b s [ j@ / n Û ¼e ¦ Y Us ³ ðr
è \ e # Q" f 0 l qÒ o + þ AF g ^ Ð & h 6 x| ¨ c 0 p x$ í s e ` ¦ כ s
.
Y
c p w à U Ø ô
[1] S. Okamoto and H. Yamamoto, J. Appl. Phys. 91, 5492 (2002).
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[4] E. Pinel, P. Boutinaid, R. Mahiou and J. Alloy.
Compd. 380, 225 (2004).
[5] J. K. Park, H. Ryu, H. D. Park and S. Y. Choi, J.
European Ceram. Doc. 21, 535 (2001).
[6] C. C. Klick and J. H. Schulman, Luminesence in Solid Soild State Physics, 5th editions, F. Seitz and D. Turnbull, (Academic Press., New York, 1957).
[7] Y. C. Kang, S. B. Park, I.W. Lenggor and K.
Okuyama, J, Phys. Chem. Solids 60, 379 (1999) [8] H. K. Yang, K. S. Shim, S. B. Kim and J. H. Jeong,
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Holloway, J. Vac. Sci. Technol. A 22, 1746 (2004).
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22, 1063 (1954).
Photoluminescence Characteristics of Zn 2−x SiO 4 :Mn 2+ x Ceramic Phosphors
Dong Woo Kim
Department of Chemistry, Silla University, Busan 617-736
Soung Soo Yi ∗
Department of Electronic Materials Engineering, Silla University, Busan 617-736 (Received 24 December 2007)
Zn
2−xSiO
4:Mn
2+xceramic phosphors for display applications were synthesized at a sintering tem- perature 1200
◦C by using a solid state reaction method. The crystallinity, surface morphology, and photoluminescence characteristics of the phosphors were investigated as a function of Mn
2+ion concentration by using X-ray diffraction, scanning electron microscopy, and luminescence spec- trophotometry. According to the results of X-ray diffraction, the (113) and the (410) directions were the preferred orientations, and the ceramics showed polycrystalline structures with (220), (223), and (110) peaks. As the concentration of Mn
2+ion increased, not only was the crystallinity of the ceramic improved but also the particle size increased and became uniform. With increasing concentration of Mn
2+ions to x=0.03, the photoluminescent intensity of the Zn
2−xSiO
4:Mn
2+xce- ramic was highest at x=0.03 and was enhanced because of not only the improved crystallinity but also the enlarged particle size of ceramics.
PACS numbers: 78.55.-m, 78.20.-e
Keywords: Zn
2SiO
4:Mn
2+, Ceramic phosphor, Photoluminescence
∗
